U.S. patent application number 13/689514 was filed with the patent office on 2013-06-20 for polymer templated nanowire catalysts.
This patent application is currently assigned to SILURIA TECHNOLOGIES, INC.. The applicant listed for this patent is Siluria Technologies, Inc.. Invention is credited to Marian Alcid, Joel M. Cizeron, Joel Gamoras, Jarod McCormick, Greg Nyce, Anja Rumplecker, Wayne P. Schammel, Erik C. Scher, Fabio R. Zurcher.
Application Number | 20130158322 13/689514 |
Document ID | / |
Family ID | 47436188 |
Filed Date | 2013-06-20 |
United States Patent
Application |
20130158322 |
Kind Code |
A1 |
Nyce; Greg ; et al. |
June 20, 2013 |
POLYMER TEMPLATED NANOWIRE CATALYSTS
Abstract
Nanowires useful as heterogeneous catalysts are provided. The
nanowire catalysts are prepared by polymer templated methods and
are useful in a variety of catalytic reactions, for example, the
oxidative coupling of methane to ethane and/or ethylene. Related
methods for use and manufacture of the same are also disclosed.
Inventors: |
Nyce; Greg; (Pleasanton,
CA) ; Scher; Erik C.; (San Francisco, CA) ;
Zurcher; Fabio R.; (Brisbane, CA) ; Cizeron; Joel
M.; (Sunnyvale, CA) ; Schammel; Wayne P.; (San
Francisco, CA) ; Gamoras; Joel; (Vallejo, CA)
; Rumplecker; Anja; (San Francisco, CA) ;
McCormick; Jarod; (San Francisco, CA) ; Alcid;
Marian; (San Francisco, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Siluria Technologies, Inc.; |
San Francisco |
CA |
US |
|
|
Assignee: |
SILURIA TECHNOLOGIES, INC.
San Francisco
CA
|
Family ID: |
47436188 |
Appl. No.: |
13/689514 |
Filed: |
November 29, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61651399 |
May 24, 2012 |
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61564834 |
Nov 29, 2011 |
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61564836 |
Nov 29, 2011 |
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Current U.S.
Class: |
585/330 ;
423/263; 423/592.1; 423/593.1; 423/594.16; 423/636; 585/661;
585/662 |
Current CPC
Class: |
B01J 37/10 20130101;
C01F 5/02 20130101; C07C 2523/10 20130101; B01J 37/08 20130101;
C01P 2002/72 20130101; C07C 2523/02 20130101; C01G 45/02 20130101;
C07C 2521/10 20130101; Y02P 20/52 20151101; C01F 17/206 20200101;
C07C 2523/30 20130101; C07C 2523/34 20130101; C01P 2004/16
20130101; C01F 5/14 20130101; C01P 2006/12 20130101; C01F 5/08
20130101; C07C 2523/04 20130101; C01P 2004/54 20130101; Y10S
977/762 20130101; C07C 11/04 20130101; B01J 23/30 20130101; C01G
45/1221 20130101; C07C 2523/22 20130101; B01J 35/0013 20130101;
C01G 25/02 20130101; C01P 2004/04 20130101; B01J 23/22 20130101;
B01J 37/031 20130101; B01J 23/10 20130101; C01G 31/02 20130101;
B01J 23/34 20130101; B82Y 30/00 20130101; C01P 2002/52 20130101;
C01P 2004/80 20130101; C07C 2521/06 20130101; B01J 21/10 20130101;
C07C 2/84 20130101; B01J 21/066 20130101; B01J 35/06 20130101; B01J
23/02 20130101; B01J 23/04 20130101; B01J 37/0018 20130101; C07C
2/84 20130101; C07C 11/04 20130101 |
Class at
Publication: |
585/330 ;
585/661; 585/662; 423/592.1; 423/593.1; 423/263; 423/636;
423/594.16 |
International
Class: |
C01F 17/00 20060101
C01F017/00; C01F 5/14 20060101 C01F005/14; C01F 5/08 20060101
C01F005/08 |
Claims
1. A method for preparing a nanowire comprising a metal oxide, a
metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the
method comprising: a) providing a solution comprising a plurality
of polymer templates; (b) introducing at least one metal ion and at
least one anion to the solution under conditions and for a time
sufficient to allow for nucleation and growth of a nanowire
comprising a plurality of metal salts (M.sub.mX.sub.nZ.sub.p) on
the template; and (c) optionally converting the nanowire
(M.sub.mX.sub.nZ.sub.p) to a metal oxide nanowire comprising a
plurality of metal oxides (M.sub.xO.sub.y), metal oxy-hydroxides
(M.sub.xO.sub.yOH.sub.z), metal oxycarbonates
(M.sub.xO.sub.y(CO.sub.3).sub.z), metal carbonate
(M.sub.x(CO.sub.3).sub.y) or combinations thereof wherein: M is, at
each occurrence, independently a metal element from any of Groups 1
through 7, lanthanides or actinides; X is, at each occurrence,
independently hydroxide, carbonate, bicarbonate, phosphate,
hydrogenphosphate, dihydrogenphosphate, sulfate, nitrate or
oxalate; Z is O; n, m, x and y are each independently a number from
1 to 100; and p is a number from 0 to 100.
2. The method of claim 1, wherein the polymer template comprises
PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyethers,
polyesters, polyamides, dextran, sugar polymers, functionalized
hydrocarbon polymers, functionalized polystyrene, polylactic acid,
polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-polypropylene glycol)-poly(ethylene glycol) or copolymers
or combinations thereof.
3. The method of claim 1, further comprising freeze drying the
nanowire.
4. The method of claim 1, wherein the solution comprising the
polymer template is in the form of a gel.
5. The method of claim 4, further comprising a step of base
treatment and precipitating at least one metal.
6. The method of claim 1, further comprising use of two or more
different metal ions.
7. A method for preparing a nanowire comprising a metal oxide, a
metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the
method comprises: a) providing a solution comprising a plurality of
a multifunctional coordinating ligands; (b) introducing at least
one metal ion to the solution, thereby forming a metal ion-ligand
complex; and (c) introducing a polyalcohol to the solution, wherein
the polyalcohol polymerizes with the metal-ion ligand complex to
form a polymerized metal ion-ligand complex.
8. The method of claim 7, wherein the multifunctional coordinating
ligand is an alpha-hydroxycarboxylic acid.
9. The method of claim 8, wherein the multifunctional coordinating
ligand is citric acid.
10. The method of claim 7, wherein the polyalcohol is ethylene
glycol or glycerol.
11. The method of claim 7 further comprising heating the
polymerized metal ion-ligand complex to remove substantially all
organic material.
12. The method of claim 7 further comprising heating the
polymerized metal ion-ligand complex to obtain a metal oxide.
13. A method for preparing metal oxide, metal oxy-hydroxide, metal
oxycarbonate or metal carbonate catalytic nanowires in a core/shell
structure, the method comprising: (a) providing a solution that
includes a plurality of polymer templates; (b) introducing a first
metal ion and a first anion to the solution under conditions and
for a time sufficient to allow for nucleation and growth of a first
nanowire (M1.sub.m1X1.sub.n1Z.sub.p1) on the template; and (c)
introducing a second metal ion and optionally a second anion to the
solution under conditions and for a time sufficient to allow for
nucleation and growth of a second nanowire
(M2.sub.m2X2.sub.n2Z.sub.p2) on the first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1); (d) converting the first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1) and the second nanowire
(M2.sub.m2X2.sub.n2Z.sub.p2) to the respective metal oxide
nanowires (M1.sub.x1O.sub.y1) and (M2.sub.x2O.sub.y2), the
respective metal oxy-hydroxide nanowires
(M1.sub.x1O.sub.y1OH.sub.z1) and (M2.sub.x2O.sub.y2OH.sub.z2) the
respective metal oxycarbonate nanowires
(M1.sub.x1O.sub.y1(CO.sub.3).sub.z1) and
(M2.sub.x2O.sub.y2(CO.sub.3).sub.z2) or the respective metal
carbonate nanowires (M1.sub.x1(CO.sub.3).sub.y1) and
(M2.sub.x2(CO.sub.3).sub.y2), wherein: M1 and M2 are the same or
different and independently selected from a metal element; X1 and
X2 are the same or different and independently hydroxide,
carbonate, bicarbonate, phosphate, hydrogenphosphate,
dihydrogenphosphate, sulfate, nitrate or oxalate; Z is O; n1, m1n2,
m2, x1, y1, z1, x2, y2 and z2 are each independently a number from
1 to 100; and p1 and p2 are independently a number from 0 to
100.
14. The method of claim 13, wherein the polymer template comprises
PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyethers,
polyesters, polyamides, dextran, sugar polymers, functionalized
hydrocarbon polymers, functionalized polystyrene, polylactic acid,
polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers
or combinations thereof.
15. The method of claim 13, wherein M1 and M2 are different.
16. A method for preparing a catalytic nanowire, the method
comprising: admixing (A) with a mixture comprising (B) and (C);
admixing (B) with a mixture comprising (A) and (C); or admixing (C)
with a mixture comprising (A) and (B) to obtain a mixture
comprising (A), (B) and (C), wherein (A), (B), and (C) comprise,
respectively: (A) a polymer template; (B) one or more salts
comprising one or more elements selected from Groups 1 through 7,
lanthanides and actinides and hydrates thereof; and (C) one or more
anion precursors.
17. The method of claim 16, wherein the mixture comprising (B) and
(C) has been prepared by admixing (B) and (C), the mixture
comprising (A) and (C) has been prepared by admixing (A) and (C) or
the mixture comprising (A) and (B) has been prepared by admixing
(A) and (B).
18. The method of claim 16, wherein the one or more salts comprise
chlorides, bromides, iodides, nitrates, sulfates, acetates, oxides,
oxalates, oxyhalides, oxynitrates, phosphates, hydrogenphosphate,
dihydrogenphosphate or mixtures thereof.
19. The method of claim 16, wherein the one or more salts comprise
MgCl.sub.2, LaCl.sub.3, ZrCl.sub.4, WCl.sub.4, MoCl.sub.4,
MnCl.sub.2MnCl.sub.3, Mg(NO.sub.3).sub.2, La(NO.sub.3).sub.3,
ZrOCl.sub.2, Mn(NO.sub.3).sub.2, Mn(NO.sub.3).sub.3,
ZrO(NO.sub.3).sub.2, Zr(NO.sub.3).sub.4 or mixtures thereof.
20. The method of claim 16, wherein the one or more salts comprise
Mg, Ca, Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures thereof.
21. The method of claim 16, wherein the one or more anion
precursors comprises alkali metal hydroxides, alkaline earth metal
hydroxides, carbonates, bicarbonates, ammonium hydroxides, or
mixtures thereof.
22. The method of claim 21, wherein the one or more anion
precursors comprises LiOH, NaOH, KOH, Sr(OH).sub.2, Ba(OH).sub.2,
Na.sub.2CO.sub.3, K.sub.2CO.sub.3, NaHCO.sub.3, KHCO.sub.3, and
NR.sub.4OH, wherein R is selected from H, and C.sub.1-C.sub.6
alkyl.
23. The method of claim 16, wherein the polymer template comprises
PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyethers,
polyesters, polyamides, dextran, sugar polymers, functionalized
hydrocarbon polymers, functionalized polystyrene, polylactic acid,
polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-polypropylene glycol)-poly(ethylene glycol) or copolymers
or combinations thereof.
24. The method of claim 16, further comprising allowing the mixture
comprising (A), (B), and (C) to stand at a temperature of from
about 4.degree. C. to about 80.degree. C. for a period of time
sufficient to allow nucleation of the catalytic nanowires
25. The method of claim 16, further comprising adding a doping
element comprising metal elements, semi-metal elements, non-metal
elements or combinations thereof to the mixture comprising (A),
(B), and (C).
26. The method of claim 16, further comprising calcining the
nanowires.
27. The method of claim 26, wherein calcining the nanowires
comprises heating the nanowires at 450.degree. C. or greater for at
least 60 min.
28. The method of claim 16, further comprising doping the
nanowires, wherein doping the nanowires comprises contacting the
nanowires with a solution comprising a dopant and evaporating any
excess liquid, wherein the dopant comprises a metal element, a
semi-metal element, a non-metal element or combinations
thereof.
29. A method for preparing metal oxide nanowires, the method
comprising: (a) providing a solution comprising a plurality of
polymer templates; and (b) introducing a compound comprising a
metal to the solution under conditions and for a time sufficient to
allow for nucleation and growth of a nanowire (M.sub.mY.sub.n) on
the template; wherein: M is a metal element from any of Groups 1
through 7, lanthanides or actinides; Y is O, n and m are each
independently a number from 1 to 100.
30. The method of claim 29, wherein the polymer template comprises
PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyethers,
polyesters, polyamides, dextran, sugar polymers, functionalized
hydrocarbon polymers, functionalized polystyrene, polylactic acid,
polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers
or combinations thereof.
31. A nanowire prepared according to the method of claim 1.
32. A catalytic material comprising the nanowire of claim 31.
33. A method for the preparation of a downstream product of
ethylene, the method comprising converting methane into ethylene in
the presence of the nanowire of claim 31 and further oligomerizing
the ethylene to prepare a downstream product of ethylene.
34. A process for the preparation of ethylene from methane
comprising contacting a mixture comprising oxygen and methane at a
temperature below 900.degree. C. with the nanowire of claim 31.
35. The method of any of claim 16, wherein the polymer template is
functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol or thiol groups.
36. The method of claim 35, wherein the polymer template comprises
a hydrocarbon polymer or a polystyrene polymer.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit under 35 U.S.C.
.sctn.119(e) of U.S. Provisional Patent Application No. 61/564,834,
filed on Nov. 29, 2011; Provisional Patent Application No.
61/564,836, filed on Nov. 29, 2011; and U.S. Provisional Patent
Application No. 61/651,399, filed on May 24, 2012; each of which
are incorporated herein by reference in their entireties.
BACKGROUND
[0002] 1. Technical Field
[0003] This invention is generally related to novel nanowire
catalysts and, more specifically, to nanowires prepared via polymer
templated methods. The nanowires are useful as heterogeneous
catalysts in a variety of catalytic reactions, such as the
oxidative coupling of methane to ethylene.
[0004] 2. Description of the Related Art
[0005] Catalysis is the process in which the rate of a chemical
reaction is either increased or decreased by means of a catalyst.
Positive catalysts increase the speed of a chemical reaction, while
negative catalysts slow it down. Substances that increase the
activity of a catalyst are referred to as promoters or activators,
and substances that deactivate a catalyst are referred to as
catalytic poisons or deactivators. Unlike other reagents, a
catalyst is not consumed by the chemical reaction, but instead
participates in multiple chemical transformations. In the case of
positive catalysts, the catalytic reaction generally has a lower
rate-limiting free energy change to the transition state than the
corresponding uncatalyzed reaction, resulting in an increased
reaction rate at the same temperature. Thus, at a given
temperature, a positive catalyst tends to increase the yield of
desired product while decreasing the yield of undesired side
products. Although catalysts are not consumed by the reaction
itself, they may be inhibited, deactivated or destroyed by
secondary processes, resulting in loss of catalytic activity.
[0006] Catalysts are generally characterized as either
heterogeneous or homogeneous. Heterogeneous catalysts exist in a
different phase than the reactants (e.g. a solid metal catalyst and
gas phase reactants), and the catalytic reaction generally occurs
on the surface of the heterogeneous catalyst. Thus, for the
catalytic reaction to occur, the reactants must diffuse to and/or
adsorb onto the catalyst surface. This transport and adsorption of
reactants is often the rate limiting step in a heterogeneous
catalysis reaction. Heterogeneous catalysts are also generally
easily separable from the reaction mixture by common techniques
such as filtration or distillation.
[0007] In contrast to a heterogeneous catalyst, a homogenous
catalyst exists in the same phase as the reactants (e.g., a soluble
organometallic catalyst and solvent-dissolved reactants).
Accordingly, reactions catalyzed by a homogeneous catalyst are
controlled by different kinetics than a heterogeneously catalyzed
reaction. In addition, homogeneous catalysts can be difficult to
separate from the reaction mixture.
[0008] While catalysis is involved in any number of technologies,
one particular area of importance is the petrochemical industry. At
the foundation of the modern petrochemical industry is the
energy-intensive endothermic steam cracking of crude oil. Cracking
is used to produce nearly all the fundamental chemical
intermediates in use today. The amount of oil used for cracking and
the volume of green house gases (GHG) emitted in the process are
quite large: cracking consumes nearly 10% of the total oil
extracted globally and produces 200 M metric tons of CO.sub.2
equivalent every year (Ren, T, Patel, M. Res. Conserv. Recycl.
53:513, 2009). There remains a significant need in this field for
new technology directed to the conversion of unreactive
petrochemical feedstocks (e.g. paraffins, methane, ethane, etc.)
into reactive chemical intermediates (e.g. olefins), particularly
with regard to highly selective heterogeneous catalysts for the
direct oxidation of hydrocarbons.
[0009] While there are multistep paths to convert methane to
certain specific chemicals using first; high temperature steam
reforming to syngas (a mixture of H.sub.2 and CO), followed by
stochiometry adjustment and conversion to either methanol or, via
the Fischer-Tropsch (F-T) synthesis, to liquid hydrocarbon fuels
such as diesel or gasoline, this does not allow for the formation
of certain high value chemical intermediates. This multi-step
indirect method also requires a large capital investment in
facilities and is expensive to operate, in part due to the energy
intensive endothermic reforming step. (For instance, in methane
reforming, nearly 40% of methane is consumed as fuel for the
reaction.) It is also inefficient in that a substantial part of the
carbon fed into the process ends up as the GHG CO.sub.2, both
directly from the reaction and indirectly by burning fossil fuels
to heat the reaction. Thus, to better exploit the natural gas
resource, direct methods that are more efficient, economical and
environmentally responsible are required.
[0010] One of the reactions for direct natural gas activation and
its conversion into a useful high value chemical, is the oxidative
coupling of methane ("OCM") to ethylene:
2CH.sub.4+O.sub.2.fwdarw.C.sub.2H.sub.4+2H.sub.2O. See, e.g.,
Zhang, Q., Journal of Natural Gas Chem., 12:81, 2003; Olah, G.
"Hydrocarbon Chemistry", Ed. 2, John Wiley & Sons (2003). This
reaction is exothermic (.DELTA.H=-67 kcals/mole) and has typically
been shown to occur at very high temperatures (>700.degree. C.).
Although the detailed reaction mechanism is not fully
characterized, experimental evidence suggests that free radical
chemistry is involved. (Lunsford, J. Chem. Soc., Chem. Comm., 1991;
H. Lunsford, Angew. Chem., Int. Ed. Engl., 34:970, 1995). In the
reaction, methane (CH.sub.4) is activated on the catalyst surface,
forming methyl radicals which then couple in the gas phase to form
ethane (C.sub.2H.sub.6), followed by dehydrogenation to ethylene
(C.sub.2H.sub.4). Several catalysts have shown activity for OCM,
including various forms of iron oxide, V.sub.2O.sub.5, MoO.sub.3,
Co.sub.3O.sub.4, Pt--Rh, Li/ZrO.sub.2, Ag--Au, Au/Co.sub.3O.sub.4,
Co/Mn, CeO.sub.2, MgO, La.sub.2O.sub.3, Mn.sub.3O.sub.4,
Na.sub.2WO.sub.4, MnO, ZnO, and combinations thereof, on various
supports. A number of doping elements have also proven to be useful
in combination with the above catalysts.
[0011] Since the OCM reaction was first reported over thirty years
ago, it has been the target of intense scientific and commercial
interest, but the fundamental limitations of the conventional
approach to C--H bond activation appear to limit the yield of this
attractive reaction. Specifically, numerous publications from
industrial and academic labs have consistently demonstrated
characteristic performance of high selectivity at low conversion of
methane, or low selectivity at high conversion (J. A. Labinger,
Cat. Lett., 1:371, 1988). Limited by this conversion/selectivity
threshold, no OCM catalyst has been able to exceed 20-25% combined
C.sub.2 yield (i.e. ethane and ethylene), and more importantly, all
such reported yields operate at extremely high temperatures
(>800 C).
[0012] In this regard, it is believed that the low yield of desired
products (i.e. C.sub.2H.sub.4 and C.sub.2H.sub.6) is caused by the
unique homogeneous/heterogeneous nature of the reaction.
Specifically, due to the high reaction temperature, a majority of
methyl radicals escape the catalyst surface and enter the gas
phase. There, in the presence of oxygen and hydrogen, multiple side
reactions are known to take place (J. A. Labinger, Cat. Lett.,
1:371, 1988). The non-selective over-oxidation of hydrocarbons to
CO and CO.sub.2 (e.g., complete oxidation) is the principal
competing fast side reaction. Other undesirable products (e.g.
methanol, formaldehyde) have also been observed and rapidly react
to form CO and CO.sub.2.
[0013] In order to result in a commercially viable OCM process, a
catalyst optimized for the activation of the C--H bond of methane
at lower temperatures (e.g. 500-700.degree. C.), higher activities
and higher pressures are required. While the above discussion has
focused on the OCM reaction, numerous other catalytic reactions (as
discussed in greater detail below) would significantly benefit from
catalytic optimization.
[0014] One type of catalyst expected to meet the above need are
nanowire catalysts comprising various metal elements; however,
methods for preparation of nanowire catalysts which fulfill these
needs are not readily available in the art. Accordingly, there
remains a need in the art for improved catalysts and, more
specifically, a need for novel approaches to catalyst preparation
and design for improving the yield of, for example, the OCM
reaction and other catalyzed reactions. The present invention
fulfills these needs and provides further related advantages.
BRIEF SUMMARY
[0015] As noted above, the present disclosure is directed to
nanowires, in particular nanowires prepared via polymer template
methods. The nanowires find utility as catalysts in any number of
chemical reactions, for example in the oxidative coupling of
methane. In one embodiment the disclosure provides a method for
preparing a nanowire comprising a metal oxide, a metal
oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the
method comprising:
[0016] a) providing a solution comprising a plurality of polymer
templates;
[0017] (b) introducing at least one metal ion and at least one
anion to the solution under conditions and for a time sufficient to
allow for nucleation and growth of a nanowire comprising a
plurality of metal salts (M.sub.mX.sub.nZ.sub.p) on the template;
and
[0018] (c) optionally converting the nanowire
(M.sub.mX.sub.nZ.sub.p) to a metal oxide nanowire comprising a
plurality of metal oxides (M.sub.xO.sub.y), metal oxy-hydroxides
(M.sub.xO.sub.yOH.sub.z), metal oxycarbonates
(M.sub.xO.sub.y(CO.sub.3).sub.z), metal carbonate
(M.sub.x(CO.sub.3).sub.y) or combinations thereof
[0019] wherein:
[0020] M is, at each occurrence, independently a metal element from
any of Groups 1 through 7, lanthanides or actinides;
[0021] X is, at each occurrence, independently hydroxides,
carbonates, bicarbonates, phosphates, hydrogenphosphates,
dihydrogenphosphates, sulfates, nitrates or oxalates;
[0022] Z is O;
[0023] n, m, x and y are each independently a number from 1 to 100;
and
[0024] p is a number from 0 to 100.
[0025] In certain embodiments of the foregoing method, the polymer
template comprises PVP (polyvinlpyrrolidone), PVA
(polyvinylalcohol), PEI (polyethyleneimine), PEG
(polyethyleneglycol), polyethers, polyesters, polyamides, dextran,
sugar polymers, functionalized hydrocarbon polymers, functionalized
polystyrene, polylactic acid, polycaprolactone, polyglycolic acid,
poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol)
or copolymers or combinations thereof. For example, in some
embodiments the polymer template is functionalized with at least
one of amine, carboxylic acid, sulfate, alcohol, halogen or thiol
groups, and in other embodiments the polymer template comprises a
hydrocarbon polymer or a polystyrene polymer functionalized with at
least one of amine, carboxylic acid, sulfate, alcohol, halogen or
thiol groups.
[0026] In other embodiments, the method further comprises freeze
drying the nanowire, and in some embodiments the solution
comprising the polymer template is in the form of a gel, for
example, some embodiments comprise a step of base treatment, for
example base treatment of a gel, and precipitating at least one
metal.
[0027] In other embodiments of the foregoing method, the method
further comprises use of two or more different metal ions.
[0028] In another aspect, the present disclosure is directed to a
method for preparing a nanowire comprising a metal oxide, a metal
oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the
method comprises:
[0029] a) providing a solution comprising a plurality of a
multifunctional coordinating ligands;
[0030] (b) introducing at least one metal ion to the solution,
thereby forming a metal ion-ligand complex; and
[0031] (c) introducing a polyalcohol to the solution, wherein the
polyalcohol polymerizes with the metal-ion ligand complex to form a
polymerized metal ion-ligand complex.
[0032] In some embodiments, the multifunctional coordinating ligand
is an alpha-hydroxycarboxylic acid. For example, in some
embodiments the multifunctional coordinating ligand is citric
acid.
[0033] In other embodiments, the polyalcohol is ethylene glycol or
glycerol.
[0034] In some embodiments, the foregoing method comprises heating
the polymerized metal ion-ligand complex to remove substantially
all organic material, while in other embodiments, the method
further comprises heating the polymerized metal ion-ligand complex
to obtain a metal oxide.
[0035] In another embodiment, the disclosure provides a method for
preparing metal oxide, metal oxy-hydroxide, metal oxycarbonate or
metal carbonate catalytic nanowires in a core/shell structure, the
method comprising:
[0036] (a) providing a solution that includes a plurality of
polymer templates;
[0037] (b) introducing a first metal ion and a first anion to the
solution under conditions and for a time sufficient to allow for
nucleation and growth of a first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1) on the template; and
[0038] (c) introducing a second metal ion and optionally a second
anion to the solution under conditions and for a time sufficient to
allow for nucleation and growth of a second nanowire
(M2.sub.m2X2.sub.n2Z.sub.p2) on the first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1);
[0039] (d) converting the first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1) and the second nanowire
(M2.sub.m2X2.sub.n2Z.sub.p2) to the respective metal oxide
nanowires (M1.sub.x1O.sub.y1) and (M2.sub.x2O.sub.y2), the
respective metal oxy-hydroxide nanowires
(M1.sub.x1O.sub.y1OH.sub.z1) and (M2.sub.x2O.sub.y2OH.sub.z2) the
respective metal oxycarbonate nanowires
(M1.sub.x1O.sub.y1(CO.sub.3).sub.z1) and
(M2.sub.x2O.sub.y2(CO.sub.3).sub.z2) or the respective metal
carbonate nanowires (M1.sub.x1(CO.sub.3).sub.y1) and
(M2.sub.x2(CO.sub.3).sub.y2),
[0040] wherein:
[0041] M1 and M2 are the same or different and independently
selected from a metal element;
[0042] X1 and X2 are the same or different and independently
hydroxides, carbonates, bicarbonates, phosphates,
hydrogenphosphates, dihydrogenphosphates, sulfates, nitrates or
oxalates;
[0043] Z is O;
[0044] n1, m1n2, m2, x1, y1, z1, x2, y2 and z2 are each
independently a number from 1 to 100; and
[0045] p1 and p2 are independently a number from 0 to 100.
[0046] In certain embodiments of the foregoing, the polymer
template comprises PVP (polyvinlpyrrolidone), PVA
(polyvinylalcohol), PEI (polyethyleneimine), PEG
(polyethyleneglycol), polyethers, polyesters, polyamides, dextran,
sugar polymers, functionalized hydrocarbon polymers, functionalized
polystyrene, polylactic acid, polycaprolactone, polyglycolic acid,
poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol)
or copolymers or combinations thereof. For example, in some
embodiments the polymer template is functionalized with at least
one of amine, carboxylic acid, sulfate, alcohol, halogen or thiol
groups, and in other embodiments the polymer template comprises a
hydrocarbon polymer or a polystyrene polymer functionalized with at
least one of amine, carboxylic acid, sulfate, alcohol, halogen or
thiol groups. In other embodiments, M1 and M2 are different.
[0047] In still other embodiments, the disclosure provides a method
for preparing a catalytic nanowire, the method comprising:
[0048] admixing (A) with a mixture comprising (B) and (C);
[0049] admixing (B) with a mixture comprising (A) and (C); or
[0050] admixing (C) with a mixture comprising (A) and (B) to obtain
a mixture comprising (A), (B) and (C), wherein (A), (B), and (C)
comprise, respectively:
[0051] (A) a polymer template;
[0052] (B) one or more salts comprising one or more elements
selected from Groups 1 through 7, lanthanides and actinides and
hydrates thereof; and
[0053] (C) one or more anion precursors.
[0054] In certain embodiments of the foregoing, the mixture
comprising (B) and (C) has been prepared by admixing (B) and (C),
the mixture comprising (A) and (C) has been prepared by admixing
(A) and (C) or the mixture comprising (A) and (B) has been prepared
by admixing (A) and (B).
[0055] In other embodiments, the one or more salts comprise
chlorides, bromides, iodides, nitrates, sulfates, acetates, oxides,
oxalates, oxyhalides, oxynitrates, phosphates, hydrogenphosphate,
dihydrogenphosphate or mixtures thereof. For example, the one or
more salts comprise MgCl.sub.2, LaCl.sub.3, ZrCl.sub.4, WCl.sub.4,
MoCl.sub.4, MnCl.sub.2MnCl.sub.3, Mg(NO.sub.3).sub.2,
La(NO.sub.3).sub.3, ZrOCl.sub.2, Mn(NO.sub.3).sub.2,
Mn(NO.sub.3).sub.3, ZrO(NO.sub.3).sub.2, Zr(NO.sub.3).sub.4 or
mixtures thereof. In other embodiments, the one or more salts
comprise Mg, Ca, Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures
thereof.
[0056] In some embodiments, the one or more anion precursors
comprises alkali metal hydroxides, alkaline earth metal hydroxides,
carbonates, bicarbonates, ammonium hydroxides, or mixtures thereof.
For example, in some embodiments the one or more anion precursors
comprises LiOH, NaOH, KOH, Sr(OH).sub.2, Ba(OH).sub.2,
Na.sub.2CO.sub.3, K.sub.2CO.sub.3, NaHCO.sub.3, KHCO.sub.3, and
NR.sub.4OH, wherein R is selected from H, and C.sub.1-C.sub.6
alkyl.
[0057] In certain other embodiments of the above method, the
polymer template comprises PVP (polyvinlpyrrolidone), PVA
(polyvinylalcohol), PEI (polyethyleneimine), PEG
(polyethyleneglycol), polyethers, polyesters, polyamides, dextran,
sugar polymers, functionalized hydrocarbon polymers, functionalized
polystyrene, polylactic acid, polycaprolactone, polyglycolic acid,
poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol)
or copolymers or combinations thereof. For example, in some
embodiments the polymer template is functionalized with at least
one of amine, carboxylic acid, sulfate, alcohol, halogen or thiol
groups, and in other embodiments the polymer template comprises a
hydrocarbon polymer or a polystyrene polymer functionalized with at
least one of amine, carboxylic acid, sulfate, alcohol, halogen or
thiol groups.
[0058] In other embodiments, the method further comprises allowing
the mixture comprising (A), (B), and (C) to stand at a temperature
of from about 4.degree. C. to about 80.degree. C. for a period of
time sufficient to allow nucleation of the catalytic nanowires, and
other examples further comprise adding a doping element comprising
metal elements, semi-metal elements, non-metal elements or
combinations thereof to the mixture comprising (A), (B), and
(C).
[0059] Some embodiments comprise calcining the nanowires, for
example in some embodiments calcining the nanowires comprises
heating the nanowires at 450.degree. C. or greater for at least 60
min.
[0060] In other embodiments, the method further comprises doping
the nanowires, wherein doping the nanowires comprises contacting
the nanowires with a solution comprising a dopant and evaporating
any excess liquid, wherein the dopant comprises a metal element, a
semi-metal element, a non-metal element or combinations
thereof.
[0061] In another embodiment, the disclosure provides a method for
preparing metal oxide nanowires, the method comprising:
[0062] (a) providing a solution comprising a plurality of polymer
templates; and
[0063] (b) introducing a compound comprising a metal to the
solution under conditions and for a time sufficient to allow for
nucleation and growth of a nanowire (M.sub.mY.sub.n) on the
template;
[0064] wherein:
[0065] M is a metal element from any of Groups 1 through 7,
lanthanides or actinides;
[0066] Y is O,
[0067] n and m are each independently a number from 1 to 100.
[0068] In some embodiments of the foregoing, the polymer template
comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyethers,
polyesters, polyamides, dextran, sugar polymers, functionalized
hydrocarbon polymers, functionalized polystyrene, polylactic acid,
polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers
or combinations thereof. For example, in some embodiments the
polymer template is functionalized with at least one of amine,
carboxylic acid, sulfate, alcohol, halogen or thiol groups, and in
other embodiments the polymer template comprises a hydrocarbon
polymer or a polystyrene polymer functionalized with at least one
of amine, carboxylic acid, sulfate, alcohol, halogen or thiol
groups.
[0069] The present disclosure also provides a nanowire prepared
according to any of the foregoing methods and in other embodiments
provides a catalytic material comprising the same.
[0070] Other embodiments provide a method for the preparation of a
downstream product of ethylene, the method comprising converting
methane into ethylene in the presence of a nanowire prepared
according to any of the foregoing methods or a catalytic material
comprising the same, and further oligomerizing the ethylene to
prepare a downstream product of ethylene.
[0071] In another embodiment, a process for the preparation of
ethylene from methane comprising contacting a mixture comprising
oxygen and methane at a temperature below 900.degree. C. with a
nanowire prepared according to any of the foregoing methods or a
catalytic material comprising the same is provided.
[0072] These and other aspects of the invention will be apparent
upon reference to the following detailed description. To this end,
various references are set forth herein which describe in more
detail certain background information, procedures, compounds and/or
compositions, and are each hereby incorporated by reference in
their entirety.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0073] In the drawings, the sizes and relative positions of
elements in the drawings are not necessarily drawn to scale. For
example, the various elements and angles are not drawn to scale,
and some of these elements are arbitrarily enlarged and positioned
to improve drawing legibility. Further, the particular shapes of
the elements as drawn are not intended to convey any information
regarding the actual shape of the particular elements, and have
been selected solely for ease of recognition in the drawings.
[0074] FIG. 1 schematically depicts a first part of an OCM reaction
at the surface of a metal oxide catalyst.
[0075] FIG. 2 shows a high throughput work flow for synthetically
generating and testing libraries of nanowires.
[0076] FIG. 3 illustrates a nanowire in one embodiment.
[0077] FIG. 4 illustrates a nanowire in a different embodiment.
[0078] FIG. 5 illustrates a plurality of nanowires.
[0079] FIG. 6 is a flow chart of an exemplary nucleation process
for forming a metal oxide nanowire.
[0080] FIG. 7 is a flow chart of an exemplary sequential nucleation
process for forming a nanowire in a core/shell configuration.
[0081] FIG. 8 schematically depicts a carbon dioxide reforming
reaction on a catalytic surface.
[0082] FIG. 9 is a flow chart for data collection and processing in
evaluating catalytic performance.
[0083] FIG. 10 illustrates a number of downstream products of
ethylene.
[0084] FIG. 11 depicts a representative process for preparing a
lithium doped MgO nanowire.
[0085] FIG. 12 depicts OCM and ethylene oligomerization
modules.
DETAILED DESCRIPTION OF THE INVENTION
[0086] In the following description, certain specific details are
set forth in order to provide a thorough understanding of various
embodiments. However, one skilled in the art will understand that
the invention may be practiced without these details. In other
instances, well-known structures have not been shown or described
in detail to avoid unnecessarily obscuring descriptions of the
embodiments. Unless the context requires otherwise, throughout the
specification and claims which follow, the word "comprise" and
variations thereof, such as, "comprises" and "comprising" are to be
construed in an open, inclusive sense, that is, as "including, but
not limited to." Further, headings provided herein are for
convenience only and do not interpret the scope or meaning of the
claimed invention.
[0087] Reference throughout this specification to "one embodiment"
or "an embodiment" means that a particular feature, structure or
characteristic described in connection with the embodiment is
included in at least one embodiment. Thus, the appearances of the
phrases "in one embodiment" or "in an embodiment" in various places
throughout this specification are not necessarily all referring to
the same embodiment. Furthermore, the particular features,
structures, or characteristics may be combined in any suitable
manner in one or more embodiments. Also, as used in this
specification and the appended claims, the singular forms "a,"
"an," and "the" include plural referents unless the content clearly
dictates otherwise. It should also be noted that the term "or" is
generally employed in its sense including "and/or" unless the
content clearly dictates otherwise.
[0088] As discussed above, heterogeneous catalysis takes place
between several phases. Generally, the catalyst is a solid, the
reactants are gases or liquids and the products are gases or
liquids. Thus, a heterogeneous catalyst provides a surface that has
multiple active sites for adsorption of one more gas or liquid
reactants. Once adsorbed, certain bonds within the reactant
molecules are weakened and dissociate, creating reactive fragments
of the reactants, e.g., in free radical forms. One or more products
are generated as new bonds between the resulting reactive fragments
form, in part, due to their proximity to each other on the
catalytic surface.
[0089] As an example, FIG. 1 shows schematically the first part of
an OCM reaction that takes place on the surface of a metal oxide
catalyst 10 which is followed by methyl radical coupling in the gas
phase. A crystal lattice structure of metal atoms 14 and oxygen
atoms 20 are shown, with an optional dopant 24 incorporated into
the lattice structure. In this reaction, a methane molecule 28
comes into contact with an active site (e.g., surface oxygen 30)
and becomes activated when a hydrogen atom 34 dissociates from the
methane molecule 28. As a result, a methyl radical 40 is generated
on or near the catalytic surface. Two methyl radicals thus
generated can couple in the gas phase to create ethane and/or
ethylene, which are collectively referred to as the "C2" coupling
products.
[0090] It is generally recognized that the catalytic properties of
a catalyst strongly correlate to its surface morphology. Typically,
the surface morphology can be defined by geometric parameters such
as: (1) the number of surface atoms (e.g., the surface oxygen of
FIG. 1) that coordinate to the reactant; and (2) the degree of
coordinative unsaturation of the surface atoms, which is the
coordination number of the surface atoms with their neighboring
atoms. For example, the reactivity of a surface atom decreases with
decreasing coordinative unsaturation. For example, for the dense
surfaces of a face-centered crystal, a surface atom with 9 surface
atom neighbors will have a different reactivity than one with 8
neighbors. Additional surface characteristics that may contribute
to the catalytic properties include, for example, crystal
dimensions, lattice distortion, surface reconstructions, defects,
grain boundaries, and the like. See, e.g., Van Santen R. A. et al
New Trends in Materials Chemistry 345-363 (1997).
[0091] Catalysts in nano-size dimensions have substantially
increased surface areas compared to their counterpart bulk
materials. The catalytic properties are expected to be enhanced as
more surface active sites are exposed to the reactants. Typically
in traditional preparations, a top-down approach (e.g., milling) is
adopted to reduce the size of the bulk material. However, the
surface morphologies of such catalysts remain largely the same as
those of the parent bulk material.
[0092] Various embodiments described herein are directed to
nanowires with controllable or tunable surface morphologies. In
particular, nanowires synthesized by a "bottom up" approach, by
which inorganic polycrystalline nanowires are nucleated from
solution phase in the presence of a template, e.g., a polymer
template. By varying the synthetic conditions, nanowires having
different compositions and/or different surface morphologies are
generated.
[0093] In contrast to a bulk catalyst of a given elemental
composition, which is likely to have a particular corresponding
surface morphology, diverse nanowires with different surface
morphologies can be generated despite having the same elemental
composition. In this way, morphologically diverse nanowires can be
created and screened according to their catalytic activity and
performance parameters in any given catalytic reaction.
Advantageously, the nanowires disclosed herein and methods of
producing the same have general applicability to a wide variety of
heterogeneous catalyses, including without limitation: oxidative
coupling of methane (e.g., FIG. 1), oxidative dehydrogenation of
alkanes to their corresponding alkenes, selective oxidation of
alkanes to alkenes and alkynes, oxidation of carbon monoxide, dry
reforming of methane, selective oxidation of aromatics,
Fischer-Tropsch reaction, hydrocarbon cracking and the like.
[0094] FIG. 2 schematically shows a high throughput work flow for
synthetically generating libraries of morphologically or
compositionally diverse nanowires and screening for their catalytic
properties. An initial phase of the work flow involves a primary
screening, which is designed to broadly and efficiently screen a
large and diverse set of nanowires that logically could perform the
desired catalytic transformation. For example, certain doped bulk
metal oxides (e.g., Li/MgO and Sr/La.sub.2O.sub.3) are known
catalysts for the OCM reaction. Therefore, nanowires of various
metal oxide compositions and/or surface morphologies can be
prepared and evaluated for their catalytic performances in an OCM
reaction.
[0095] More specifically, the work flow 100 begins with designing
synthetic experiments based on solution phase template formations
(block 110). The synthesis, subsequent treatments and screenings
can be manual or automated. As will be discussed in more detail
herein, by varying the synthetic conditions, nanowires can be
prepared with various surface morphologies and/or compositions in
respective microwells (block 114). The nanowires are subsequently
calcined and then optionally doped (block 120). Optionally, the
doped and calcined nanowires are further mixed with a catalyst
support (block 122). Beyond the optional support step, all
subsequent steps are carried out in a "wafer" format, in which
nanowire catalysts are deposited in a quartz wafer that has been
etched to create an ordered array of microwells. Each microwell is
a self-contained reactor, in which independently variable
processing conditions can be designed to include, without
limitation, respective choices of elemental compositions, catalyst
support, reaction precursors, templates, reaction durations, pH
values, temperatures, ratio between reactants, gas flows, and
calcining conditions (block 124). Due to design constraints of some
wafers, in some embodiments calcining and other temperature
variables are identical in all microwells. A wafer map 130 can be
created to correlate the processing conditions to the nanowire in
each microwell. A library of diverse nanowires can be generated in
which each library member corresponds to a particular set of
processing conditions and corresponding compositional and/or
morphological characteristics.
[0096] Nanowires obtained under various synthetic conditions are
thereafter deposited in respective microwells of a wafer (140) for
evaluating their respective catalytic properties in a given
reaction (blocks 132 and 134). The catalytic performance of each
library member can be screened serially by several known primary
screening technologies, including scanning mass spectroscopy (SMS)
(Symyx Technologies Inc., Santa Clara, Calif.). The screening
process is fully automated, and the SMS tool can determine if a
nanowire is catalytically active or not, as well as its relative
strength as a catalyst at a particular temperature. Typically, the
wafer is placed on a motion control stage capable of positioning a
single well below a probe that flows the feed of the starting
material over the nanowire surface and removes reaction products to
a mass spectrometer and/or other detector technologies (blocks 134
and 140). The individual nanowire is heated to a preset reaction
temperature, e.g., using a CO.sub.2 IR laser from the backside of
the quartz wafer and an IR camera to monitor temperature and a
preset mixture of reactant gases. The SMS tool collects data with
regard to the consumption of the reactant(s) and the generation of
the product(s) of the catalytic reaction in each well (block 144),
and at each temperature and flow rate.
[0097] The SMS data obtained as described above provide information
on relative catalytic properties among all the library members
(block 150). In order to obtain more quantitative data on the
catalytic properties of the nanowires, possible hits that meet
certain criteria are subjected to a secondary screening (block
154). Typically, secondary screening technologies include a single,
or alternatively multiple channel fixed-bed or fluidized bed
reactors (as described in more detail herein). In parallel reactor
systems or multi-channel fixed-bed reactor system, a single feed
system supplies reactants to a set of flow restrictors. The flow
restrictors divide the flows evenly among parallel reactors. Care
is taken to achieve uniform reaction temperature between the
reactors such that the various nanowires can be differentiated
solely based on their catalytic performances. The secondary
screening allows for accurate determination of catalytic properties
such as selectivity, yield and conversion. (block 160). These
results serve as a feedback for designing further nanowire
libraries. Additional description of SMS tools in a combinatorial
approach for discovering catalysts can be found in, e.g., Bergh, S.
et al. Topics in Catalysts 23:1-4, 2003.
[0098] Thus, in accordance with various embodiments described
herein, compositional and morphologically diverse nanowires can be
rationally synthesized to meet catalytic performance criteria.
These and other aspects of the present disclosure are described in
more detail below.
DEFINITIONS
[0099] As used herein, and unless the context dictates otherwise,
the following terms have the meanings as specified below.
[0100] "Catalyst" means a substance that alters the rate of a
chemical reaction. A catalyst may either increase the chemical
reaction rate (i.e. a "positive catalyst") or decrease the reaction
rate (i.e. a "negative catalyst"). Catalysts participate in a
reaction in a cyclic fashion such that the catalyst is cyclically
regenerated. "Catalytic" means having the properties of a
catalyst.
[0101] "Polymer" refers to a molecule comprised of two or more
repeating structural units (i.e., "monomers"). The structural units
are typically connected by covalent bonds. The structural units
are, at each occurrence, independently the same or different and
can be connected in any order (e.g., random, repeating, block
copolymer, etc.). An exemplary polymer is polyethylene, which can
be prepared using a process employing the disclosed nanowires.
Certain embodiments of the polymers described herein are suitable
for use as a template for forming the disclosed nanowires. Polymers
in this respect include, but are not limited to, PVP
(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyethers,
polyesters, polyamides, dextran, sugar polymers, functionalized
hydrocarbon polymers, functionalized polystyrene, polylactic acid,
polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol), copolymers
and combinations of the foregoing and the like.
[0102] "Functionalized" when used in reference to a polymer means
the polymer may be substituted with one or more functional groups.
In general, the functional groups are moieties capable of
interaction with metal ions (e.g., via coordination or other
interaction) and are useful for initiating nucleation of the
nanowires. Representative functional groups include, but are not
limited to, amine, carboxylic acid, sulfate, alcohol, halogen
(e.g., F, Cl, Br or I) and/or thiol moieties. Unless specifically
stated otherwise, the polymers described herein are optionally
functionalized (i.e., may either be unfunctionalized or
functionalized with one or more functional groups).
[0103] "Nanoparticle" means a particle having at least one diameter
on the order of nanometers (e.g. between about 1 and 100
nanometers).
[0104] "Nanowire" means a nanowire structure having at least one
diameter on the order of nanometers (e.g. between about 1 and 100
nanometers) and an aspect ratio greater than 10:1. The "aspect
ratio" of a nanowire is the ratio of the actual length (L) of the
nanowire to the diameter (D) of the nanowire. Aspect ratio is
expressed as L:D.
[0105] "Polycrystalline nanowire" means a nanowire having multiple
crystal domains. Polycrystalline nanowires generally have different
morphologies (e.g. bent vs. straight) as compared to the
corresponding "single-crystalline" nanowires.
[0106] "Effective length" of a nanowire means the shortest distance
between the two distal ends of a nanowire as measured by
transmission electron microscopy (TEM) in bright field mode at 5
keV. "Average effective length" refers to the average of the
effective lengths of individual nanowires within a plurality of
nanowires.
[0107] "Actual length" of a nanowire means the distance between the
two distal ends of a nanowire as traced through the backbone of the
nanowire as measured by TEM in bright field mode at 5 keV. "Average
actual length" refers to the average of the actual lengths of
individual nanowires within a plurality of nanowires.
[0108] The "diameter" of a nanowire is measured in an axis
perpendicular to the axis of the nanowire's actual length (i.e.
perpendicular to the nanowires backbone). The diameter of a
nanowire will vary from narrow to wide as measured at different
points along the nanowire backbone. As used herein, the diameter of
a nanowire is the most prevalent (i.e. the mode) diameter.
[0109] The "ratio of effective length to actual length" is
determined by dividing the effective length by the actual length. A
nanowire having a "bent morphology" will have a ratio of effective
length to actual length of less than one as described in more
detail herein. A straight nanowire will have a ratio of effective
length to actual length equal to one as described in more detail
herein.
[0110] "Inorganic" means a substance comprising a metal element.
Typically, an inorganic can be one or more metals in its elemental
state, or more preferably, a compound formed by a metal ion
(M.sup.n+, wherein n 1, 2, 3, 4, 5, 6 or 7) and an anion (X.sup.m-,
m is 1, 2, 3 or 4), which balance and neutralize the positive
charges of the metal ion through electrostatic interactions.
Non-limiting examples of inorganic compounds include oxides,
hydroxides, halides, nitrates, sulfates, carbonates, phosphates,
acetates, oxalates, and combinations thereof, of metal elements.
Other non-limiting examples of inorganic compounds include
Li.sub.2CO.sub.3, Li.sub.2PO.sub.4, LiOH, Li.sub.2O, LiCl, LiBr,
LiL, Li.sub.2C.sub.2O.sub.4, Li.sub.2SO.sub.4, Na.sub.2CO.sub.3,
Na.sub.2PO.sub.4, NaOH, Na.sub.2O, NaCl, NaBr, NaI,
Na.sub.2C.sub.2O.sub.4, Na.sub.2SO.sub.4, K.sub.2CO.sub.3,
K.sub.2PO.sub.4, KOH, K.sub.2O, KCl, KBr, KI,
K.sub.2C.sub.2O.sub.4, K.sub.2SO.sub.4, Cs.sub.2CO.sub.3,
CsPO.sub.4, CsOH, Cs.sub.2O, CsCl, CsBr, CsI, CsC.sub.2O.sub.4,
CsSO.sub.4, Be(OH).sub.2, BeCO.sub.3, BePO.sub.4, BeO, BeCl.sub.2,
BeBr.sub.2, BeI.sub.2, BeC.sub.2O.sub.4. BeSO.sub.4, Mg(OH).sub.2,
MgCO.sub.3, MgPO.sub.4, MgO, MgCl.sub.2, MgBr.sub.2, MgI.sub.2,
MgC.sub.2O.sub.4. MgSO.sub.4, Ca(OH).sub.2, CaO, CaCO.sub.3,
CaPO.sub.4, CaCl.sub.2, CaBr.sub.2, CaI.sub.2, Ca(OH).sub.2,
CaC.sub.2O.sub.4, CaSO.sub.4, Y.sub.2O.sub.3,
Y.sub.2(CO.sub.3).sub.3, Y.sub.2(PO.sub.4).sub.3, Y(OH).sub.3,
YCl.sub.3, YBr.sub.3, YI.sub.3, Y.sub.2(C.sub.2O4).sub.3,
Y.sub.2(SO4).sub.3, Zr(OH).sub.4, Zr(CO.sub.3).sub.2,
Zr(PO.sub.4).sub.2, ZrO(OH).sub.2, ZrO2, ZrCl.sub.4, ZrBr.sub.4,
ZrI.sub.4, Zr(C.sub.2O.sub.4).sub.2, Zr(SO.sub.4).sub.2,
Ti(OH).sub.4, TiO(OH).sub.2, Ti(CO.sub.3).sub.2,
Ti(PO.sub.4).sub.2, TiO2, TiCl.sub.4, TiBr.sub.4, TiI.sub.4,
Ti(C.sub.2O.sub.4).sub.2, Ti(SO.sub.4).sub.2, BaO, Ba(OH).sub.2,
BaCO.sub.3, BaPO.sub.4, BaCl.sub.2, BaBr.sub.2, BaI.sub.2,
BaC.sub.2O.sub.4, BaSO.sub.4, La(OH).sub.3,
La.sub.2(CO.sub.3).sub.3, La.sub.2(PO.sub.4).sub.3,
La.sub.2O.sub.3, LaCl.sub.3, LaBr.sub.3, LaI.sub.3,
La.sub.2(C.sub.2O.sub.4).sub.3, La.sub.2(SO.sub.4).sub.3,
Ce(OH).sub.4, Ce(CO.sub.3).sub.2, Ce(PO.sub.4).sub.2, CeO.sub.2,
Ce.sub.2O.sub.3, CeCl.sub.4, CeBr.sub.4, CeI.sub.4,
Ce(C.sub.2O.sub.4).sub.2, Ce(SO.sub.4).sub.2, ThO.sub.2,
Th(CO.sub.3).sub.2, Th(PO.sub.4).sub.2, ThCl.sub.4, ThBr.sub.4,
ThI.sub.4, Th(OH).sub.4, Th(C.sub.2O.sub.4).sub.2,
Th(SO.sub.4).sub.2, Sr(OH).sub.2, SrCO.sub.3, SrPO.sub.4, SrO,
SrCl.sub.2, SrBr.sub.2, SrI.sub.2, SrC.sub.2O.sub.4, SrSO.sub.4,
Sm.sub.2O.sub.3, Sm.sub.2(CO.sub.3).sub.3,
Sm.sub.2(PO.sub.4).sub.3, SmCl.sub.3, SmBr.sub.3, SmI.sub.3,
Sm(OH).sub.3, Sm.sub.2(CO3).sub.3, Sm.sub.2(C.sub.2O.sub.3).sub.3,
Sm.sub.2(SO.sub.4).sub.3, LiCa.sub.2Bi.sub.3O.sub.4Cl.sub.6,
Na.sub.2WO.sub.4, K/SrCoO.sub.3, K/Na/SrCoO.sub.3, Li/SrCoO.sub.3,
SrCoO.sub.3, molybdenum oxides, molybdenum hydroxides, molybdenum
carbonates, molybdenum phosphates, molybdenum chlorides, molybdenum
bromides, molybdenum iodides, molybdenum oxalates, molybdenum
sulfates, manganese oxides, manganese chlorides, manganese
bromides, manganese iodides, manganese hydroxides, manganese
oxalates, manganese sulfates, manganese tugstates, vanadium oxides,
vanadium carbonates, vanadium phosphates, vanadium chlorides,
vanadium bromides, vanadium iodides, vanadium hydroxides, vanadium
oxalates, vanadium sulfates, tungsten oxides, tungsten carbonates,
tungsten phosphates, tungsten chlorides, tungsten bromides,
tungsten iodides, tungsten hydroxides, tungsten oxalates, tungsten
sulfates, neodymium oxides, neodymium carbonates, neodymium
phosphates, neodymium chlorides, neodymium bromides, neodymium
iodides, neodymium hydroxides, neodymium oxalates, neodymium
sulfates, europium oxides, europium carbonates, europium
phosphates, europium chlorides, europium bromides, europium
iodides, europium hydroxides, europium oxalates, europium sulfates
rhenium oxides, rhenium carbonates, rhenium phosphates, rhenium
chlorides, rhenium bromides, rhenium iodides, rhenium hydroxides,
rhenium oxalates, rhenium sulfates, chromium oxides, chromium
carbonates, chromium phosphates, chromium chlorides, chromium
bromides, chromium iodides, chromium hydroxides, chromium oxalates,
chromium sulfates, potassium molybdenum oxides and the like.
[0111] "Salt" means a compound comprising negative and positive
ions. Salts are generally comprised of cations and counter ions.
Under appropriate conditions, e.g., the solution also comprises a
template, the metal ion (M.sup.n+) and the anion (X.sup.m-) bind to
the template to induce nucleation and growth of a nanowire of
M.sub.mX.sub.n on the template. "Anion precursor" thus is a
compound that comprises an anion and a cationic counter ion, which
allows the anion (X.sup.m-) dissociate from the cationic counter
ion in a solution. Specific examples of the metal salt and anion
precursors are described in further detail herein.
[0112] "Oxide" refers to a metal compound comprising oxygen.
Examples of oxides include, but are not limited to, metal oxides
(M.sub.xO.sub.y), metal oxyhalides (M.sub.xO.sub.yX.sub.z), metal
oxynitrates (M.sub.xO.sub.y(NO.sub.3).sub.z), metal phosphates
(M.sub.x(PO.sub.4).sub.y), metal oxycarbonates
(M.sub.xO.sub.y(CO.sub.3).sub.z), metal carbonates, metal
oxyhydroxides (M.sub.xO.sub.y(OH).sub.z) and the like, wherein x, y
and z are numbers from 1 to 100.
[0113] "Crystal domain" means a continuous region over which a
substance is crystalline.
[0114] "Single-crystalline nanowires" means a nanowire having a
single crystal domain.
[0115] "Template" is any synthetic and/or natural material that
provides at least one nucleation site where ions can nucleate and
grow to form nanoparticles. In certain embodiments, the templates
comprise polymers. Typically, the polymer comprises multiple
binding sites that recognize certain ions and allow for the
nucleation and growth of the same. Non-limiting examples of
templates include the polymers described herein.
[0116] "Nucleation" refers to the process of forming a solid from
solubilized particles, for example forming a nanowire in situ by
converting a soluble precursor (e.g. metal and hydroxide ions) into
nanocrystals in the presence of a template.
[0117] "Nucleation site" refers to a site on a template, for
example a polymer, where nucleation of ions may occur. Nucleation
sites include, for example, amino acids having carboxylic acid
(--COOH), amino (--NH.sub.3.sup.+ or --NH.sub.2), hydroxyl (--OH),
and/or thiol (--SH) functional groups.
[0118] "Anisotropic" means having an aspect ratio greater than
one.
[0119] "Turnover number" is a measure of the number of reactant
molecules a catalyst can convert to product molecules per unit
time.
[0120] "Dopant" or "doping agent" is an impurity added to or
incorporated within a catalyst to optimize catalytic performance
(e.g. increase or decrease catalytic activity). As compared to the
undoped catalyst, a doped catalyst may increase or decrease the
selectivity, conversion, and/or yield of a reaction catalyzed by
the catalyst.
[0121] "Atomic percent" (at % or at/at) or "atomic ratio" when used
in the context of nanowire dopants refers to the ratio of the total
number of dopant atoms to the total number of metal atoms in the
nanowire. For example, the atomic percent of dopant in a lithium
doped Mg.sub.6MnO.sub.8 nanowire is determined by calculating the
total number of lithium atoms and dividing by the sum of the total
number of magnesium and manganese atoms and multiplying by 100
(i.e., atomic percent of dopant=[Li atoms/(Mg atoms+Mn
atoms)].times.100).
[0122] "Weight percent" (wt/wt)" when used in the context of
nanowire dopants refers to the ratio of the total weight of dopant
to the total combined weight of thedopant and the nanowire. For
example, the weight percent of dopant in a lithium doped
Mg.sub.6MnO.sub.8 nanowire is determined by calculating the total
weight of lithium and dividing by the sum of the total combined
weight of lithium and Mg.sub.6MnO.sub.8 and multiplying by 100
(i.e., weight percent of dopant=[Li weight/(Li
weight+Mg.sub.6MnO.sub.8 weight)].times.100).
[0123] "Group 1" elements include lithium (Li), sodium (Na),
potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
[0124] "Group 2" elements include beryllium (Be), magnesium (Mg),
calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
[0125] "Group 3" elements include scandium (Sc) and yttrium
(Y).
[0126] "Group 4" elements include titanium (Ti), zirconium (Zr),
halfnium (Hf), and rutherfordium (Rf).
[0127] "Group 5" elements include vanadium (V), niobium (Nb),
tantalum (Ta), and dubnium (Db).
[0128] "Group 6" elements include chromium (Cr), molybdenum (Mo),
tungsten (W), and seaborgium (Sg).
[0129] "Group 7" elements include manganese (Mn), technetium (Tc),
rhenium (Re), and bohrium (Bh).
[0130] "Group 8" elements include iron (Fe), ruthenium (Ru), osmium
(Os), and hassium (Hs).
[0131] "Group 9" elements include cobalt (Co), rhodium (Rh),
iridium (Ir), and meitnerium (Mt).
[0132] "Group 10" elements include nickel (Ni), palladium (Pd),
platinum (Pt) and darmistadium (Ds).
[0133] "Group 11" elements include copper (Cu), silver (Ag), gold
(Au), and roentgenium (Rg).
[0134] "Group 12" elements include zinc (Zn), cadmium (Cd), mercury
(Hg), and copernicium (Cn).
[0135] "Lanthanides" include lanthanum (La), cerium (Ce),
praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm),
europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy),
holmium (Ho), erbium (Er), thulium (Tm), yitterbium (Yb), and
lutetium (Lu).
[0136] "Actinides" include actinium (Ac), thorium (Th),
protactinium (Pa), uranium (U), neptunium (Np), plutonium (Pu),
americium (Am), curium (Cm), berklelium (Bk), californium (Cf),
einsteinium (Es), fermium (Fm), mendelevium (Md), nobelium (No),
and lawrencium (Lr).
[0137] "Metal element" or "metal" is any element, except hydrogen,
selected from Groups 1 through 12, lanthanides, actinides, aluminum
(Al), gallium (Ga), indium (In), tin (Sn), thallium (Tl), lead
(Pb), and bismuth (Bi). Metal elements include metal elements in
their elemental form as well as metal elements in an oxidized or
reduced state, for example, when a metal element is combined with
other elements in the form of compounds comprising metal elements.
For example, metal elements can be in the form of hydrates, salts,
oxides, as well as various polymorphs thereof, and the like.
[0138] "Semi-metal element" refers to an element selected from
boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony
(Sb), tellurium (Te), and polonium (Po).
[0139] "Non-metal element" refers to an element selected from
carbon (C), nitrogen (N), oxygen (O), fluorine (F), phosphorus (P),
sulfur (S), chlorine (Cl), selenium (Se), bromine (Br), iodine (I),
and astatine (At).
[0140] "C.sub.2" refers to a hydrocarbon (i.e., compound consisting
of carbon and hydrogen atoms) having only two carbon atoms, for
example ethane and ethylene. Similarily, "C3" refers to a
hydrocarbon having only 3 carbon atoms, for example propane and
propylene.
[0141] "Conversion" means the mole fraction (i.e., percent) of a
reactant converted to a product or products.
[0142] "Selectivity" refers to the percent of converted reactant
that went to a specified product, e.g., C2 selectivity is the % of
converted methane that formed ethane and ethylene, C3 selectivity
is the % of converted methane that formed propane and propylene, CO
selectivity is the % of converted methane that formed CO.
[0143] "Yield" is a measure of (e.g. percent) of product obtained
relative to the theoretical maximum product obtainable. Yield is
calculated by dividing the amount of the obtained product in moles
by the theoretical yield in moles. Percent yield is calculated by
multiplying this value by 100. C2 yield is defined as the sum of
the ethane and ethylene molar flow at the reactor outlet multiplied
by two and divided by the inlet methane molar flow. C3 yield is
defined as the sum of propane and propylene molar flow at the
reactor outlet multiplied by three and divided by the inlet methane
molar flow. C2+ yield is the sum of the C2 yield and C3 yield.
Yield is also calculable by multiplying the methane conversion by
the relevant selectivity, e.g. C2 yield is equal to the methane
conversion times the C2 selectivity.
[0144] "Bulk catalyst" or "bulk material" means a catalyst prepared
by traditional techniques, for example by milling or grinding large
catalyst particles to obtain smaller/higher surface area catalyst
particles. Bulk materials are prepared with minimal control over
the size and/or morphology of the material.
[0145] "Alkane" means a straight chain or branched, noncyclic or
cyclic, saturated aliphatic hydrocarbon. Alkanes include linear,
branched and cyclic structures. Representative straight chain
alkanes include methane, ethane, n-propane, n-butane, n-pentane,
n-hexane, and the like; while branched alkanes include isopropane,
sec-butane, isobutanel, tert-butane, isopentane, and the like.
Representative cyclic alkanes include cyclopropane, cyclobutane,
cyclopentane, cyclohexane, and the like. "Alkene" means a straight
chain or branched, noncyclic or cyclic, unsaturated aliphatic
hydrocarbon having at least one carbon-carbon double bond. Alkenes
include linear, branched and cyclic structures. Representative
straight chain and branched alkenes include ethylene, propylene,
1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene,
3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, and
the like. Cyclic alkenes include cyclohexene and cyclopentene and
the like.
[0146] "Alkyne" means a straight chain or branched, noncyclic or
cyclic, unsaturated aliphatic hydrocarbon having at least one
carbon-carbon triple bond. Alkynes include linear, branched and
cyclic structures. Representative straight chain and branched
alkynes include acetylene, propyne, 1-butyne, 2-butyne, 1-pentyne,
2-pentyne, 3-methyl-1-butyne, and the like. Representative cyclic
alkynes include cycloheptyne and the like.
[0147] "Alkyl," "alkenyl" and "alkynyl" refers to an alkane, alkene
or alkyne radical, respectively.
[0148] "Aromatic" means a carbocyclic moiety having a cyclic system
of conjugated p orbitals forming a delocalized conjugated .pi.
system and a number of .pi. electrons equal to 4n+2 with n=0, 1, 2,
3, etc. Representative examples of aromatics include benzene and
naphthalene and toluene. "Aryl" refers to an aromatic radical.
Exemplary aryl groups include, but are not limited to, phenyl,
napthyl and the like.
[0149] "Carbon-containing compounds" are compounds that comprise
carbon. Non-limiting examples of carbon-containing compounds
include hydrocarbons, CO and CO.sub.2.
[0150] 1. Structure/Physical Characteristics
[0151] As noted above, disclosed herein are nanowires useful as
catalysts. Catalytic nanowires, and methods for preparing the same,
are also described in PCT Pub. No. 2011/149996 and U.S. application
Ser. No. ______, filed on Nov. 29, 2012, and entitled "Nanowire
Catalysts and Methods For Their Use and Preparation," the full
disclosures of which are incorporated herein by reference in their
entireties. FIG. 3 is a schematic representation of a
representative nanowire 200. Typically, the nanowire is not uniform
in its thickness or diameter. At any given location along the
nanowire backbone, a diameter (240a, 240b, 240c, 240d) is the
longest dimension of a cross section of the nanowire, i.e., is
perpendicular to the axis of the nanowire backbone). FIG. 4 is a
schematic representation of the nanowire 250, which shows
non-uniform diameters (280a, 280b, 280c and 280d).
[0152] As noted above, in some embodiments nanowires having a
"bent" morphology (i.e. "bent nanowires") are provided. A "bent`
morphology means that the bent nanowires comprise various twists,
bends and/or kinks in their general morphology as illustrated
generally in FIG. 3 and discussed above. Bent nanowires have a
ratio of effective length to actual length of less than one.
Accordingly, in some embodiments the present disclosure provides
nanowires having a ratio of effective length to actual length of
less than one. In other embodiments, the nanowires have a ratio of
effective length to actual length of between 0.99 and 0.01, between
0.9 and 0.1, between 0.8 and 0.2, between 0.7 and 0.3, or between
0.6 and 0.4. In other embodiments, the ratio of effective length to
actual length is less than 0.99, less than 0.9, less than 0.8, less
than 0.7, less than 0.6, less than 0.5, less than 0.4, less than
0.3, less than 0.2 or less than 0.1. In other embodiments, the
ratio of effective length to actual length is less than 1.0 and
more than 0.9, less than 1.0 and more than 0.8, less than 1.0 and
more than 0.7, less than 1.0 and more than 0.6, less than 1.0 and
more than 0.5, less than 1.0 and more than 0.4, less than 1.0 and
more than 0.3, less than 1.0 and more than 0.2, or less than 1.0
and more than 0.1.
[0153] The ratio of effective length to actual length of a nanowire
having a bent morphology may vary depending on the angle of
observation. For example, one-skilled in the art will recognize
that the same nanowire, when observed from different perspectives,
can have a different effective length as determined by TEM. In
addition, not all nanowires having a bent morphology will have the
same ratio of effective length to actual length. Accordingly, in a
population (i.e. plurality) of nanowires having a bent morphology,
a range of ratios of effective length to actual length is expected.
Although the ratio of effective length to actual length may vary
from nanowire to nanowire, nanowires having a bent morphology will
always have a ratio of effective length to actual length of less
than one from any angle of observation.
[0154] In various embodiments, a substantially straight nanowire is
provided. A substantially straight nanowire has a ratio of
effective length to actual length equal to one. Accordingly, in
some embodiments, the nanowires of the present disclosure have a
ratio of effective length to actual length equal to one.
[0155] The actual lengths of the nanowires disclosed herein may
vary. For example in some embodiments, the nanowires have an actual
length of between 100 nm and 100 .mu.m. In other embodiments, the
nanowires have an actual length of between 100 nm and 10 .mu.m. In
other embodiments, the nanowires have an actual length of between
200 nm and 10 .mu.m. In other embodiments, the nanowires have an
actual length of between 500 nm and 5 .mu.m. In other embodiments,
the actual length is greater than 5 .mu.m. In other embodiments,
the nanowires have an actual length of between 800 nm and 1000 nm.
In other further embodiments, the nanowires have an actual length
of 900 nm. As noted below, the actual length of the nanowires may
be determined by TEM, for example, in bright field mode at 5
keV.
[0156] The diameter of the nanowires may be different at different
points along the nanowire backbone. However, the nanowires comprise
a mode diameter (i.e. the most frequently occurring diameter). As
used herein, the diameter of a nanowire refers to the mode
diameter. In some embodiments, the nanowires have a diameter of
between 1 nm and 10 .mu.m, between 1 nm and 1 .mu.m, between 1 nm
and 500 nm, between 1 nm and 100 nm, between 7 nm and 100 nm,
between 7 nm and 50 nm, between 7 nm and 25 nm, or between 7 nm and
15 nm. On other embodiments, the diameter is greater than 500 nm.
As noted below, the diameter of the nanowires may be determined by
TEM, for example, in bright field mode at 5 keV.
[0157] Various embodiments of the present disclosure provide
nanowires having different aspect ratios. In some embodiments, the
nanowires have an aspect ratio of greater than 10:1. In other
embodiments, the nanowires have an aspect ratio greater than 20:1.
In other embodiments, the nanowires have an aspect ratio greater
than 50:1. In other embodiments, the nanowires have an aspect ratio
greater than 100:1.
[0158] In some embodiments, the nanowires comprise a solid core
while in other embodiments, the nanowires comprise a hollow
core.
[0159] The morphology of a nanowire (including length, diameter,
and other parameters) can be determined by transmission electron
microscopy (TEM). Transmission electron microscopy (TEM) is a
technique whereby a beam of electrons is transmitted through an
ultra thin specimen, interacting with the specimen as it passes
through. An image is formed from the interaction of the electrons
transmitted through the specimen. The image is magnified and
focused onto an imaging device, such as a fluorescent screen, on a
layer of photographic film or detected by a sensor such as a CCD
camera. TEM techniques are well known to those of skill in the
art.
[0160] A TEM image of nanowires may be taken, for example, in
bright field mode at 5 keV.
[0161] The nanowires of the present disclosure can be further
characterized by powder x-ray diffraction (XRD). XRD is a technique
capable of revealing information about the crystallographic
structure, chemical composition, and physical properties of
materials, including nanowires. XRD is based on observing the
diffracted intensity of an X-ray beam hitting a sample as a
function of incident and diffraction angle, polarization, and
wavelength or energy.
[0162] Crystal structure, composition, and phase, including the
crystal domain size of the nanowires, can be determined by XRD. In
some embodiments, the nanowires comprise a single crystal domain
(i.e. single crystalline). In other embodiments, the nanowires
comprise multiple crystal domains (i.e. polycrystalline). In some
other embodiments, the average crystal domain of the nanowires is
less than 100 nm, less than 50 nm, less than 30 nm, less than 20
nm, less than 10 nm, less than 5 nm, or less than 2 nm.
[0163] Typically, a catalytic material described herein comprises a
plurality of nanowires. In certain embodiments, the plurality of
nanowires form a mesh of randomly distributed and, to various
degrees, interconnected nanowires. FIG. 5 is a schematic
representation of a nanowire mesh 300.
[0164] The total surface area per gram of a nanowire or plurality
of nanowires may have an effect on the catalytic performance. Pore
size distribution may affect the nanowires catalytic performance as
well. Surface area and pore size distribution of the nanowires or
plurality of nanowires can be determined by BET (Brunauer, Emmett,
Teller) measurements. BET techniques utilize nitrogen adsorption at
various temperatures and partial pressures to determine the surface
area and pore sizes of catalysts. BET techniques for determining
surface area and pore size distribution are well known in the
art.
[0165] In some embodiments the nanowires have a surface area of
between 0.0001 and 3000 m.sup.2/g, between 0.0001 and 2000
m.sup.2/g, between 0.0001 and 1000 m.sup.2/g, between 0.0001 and
500 m.sup.2/g, between 0.0001 and 100 m.sup.2/g, between 0.0001 and
50 m.sup.2/g, between 0.0001 and 20 m.sup.2/g, between 0.0001 and
10 m.sup.2/g or between 0.0001 and 5 m.sup.2/g.
[0166] In some embodiments the nanowires have a surface area of
between 0.001 and 3000 m.sup.2/g, between 0.001 and 2000 m.sup.2/g,
between 0.001 and 1000 m.sup.2/g, between 0.001 and 500 m.sup.2/g,
between 0.001 and 100 m.sup.2/g, between 0.001 and 50 m.sup.2/g,
between 0.001 and 20 m.sup.2/g, between 0.001 and 10 m.sup.2/g or
between 0.001 and 5 m.sup.2/g.
[0167] In some other embodiments the nanowires have a surface area
of between 2000 and 3000 m.sup.2/g, between 1000 and 2000
m.sup.2/g, between 500 and 1000 m.sup.2/g, between 100 and 500
m.sup.2/g, between 10 and 100 m.sup.2/g, between 5 and 50
m.sup.2/g, between 2 and 20 m.sup.2/g or between 0.0001 and 10
m.sup.2/g.
[0168] In other embodiments, the nanowires have a surface area of
greater than 2000 m.sup.2/g, greater than 1000 m.sup.2/g, greater
than 500 m.sup.2/g, greater than 100 m.sup.2/g, greater than 50
m.sup.2/g, greater than 20 m.sup.2/g, greater than 10 m.sup.2/g,
greater than 5 m.sup.2/g, greater than 1 m.sup.2/g, greater than
0.0001 m.sup.2/g.
[0169] 2. Chemical Composition
[0170] As noted above, disclosed herein are nanowires useful as
catalysts. The catalytic nanowires may have any number of
compositions and morphologies. In some embodiments, the nanowires
are inorganic. In other embodiments, the nanowires are
polycrystalline. In some other embodiments, the nanowires are
inorganic and polycrystalline. In yet other embodiments, the
nanowires are single-crystalline, or in other embodiments the
nanowires are inorganic and single-crystalline. In still other
embodiments of any of the foregoing, the nanowires may have a ratio
of effective length to actual length of less than one and an aspect
ratio of greater than ten as measured by TEM in bright field mode
at 5 keV. In still other embodiments of any of the forgoing, the
nanowires may comprise one or more elements from any of Groups 1
through 7, lanthanides, actinides or combinations thereof.
[0171] In some embodiments, the nanowires comprise one or more
metal elements from any of Groups 1-7, lanthanides, actinides or
combinations thereof, for example, the nanowires may be
mono-metallic, bi-metallic, tri-metallic, etc (i.e. contain one,
two, three, etc. metal elements). In some embodiments, the metal
elements are present in the nanowires in elemental form while in
other embodiments the metal elements are present in the nanowires
in oxidized form. In other embodiments the metal elements are
present in the nanowires in the form of a compound comprising a
metal element. The metal element or compound comprising the metal
element may be in the form of oxides, hydroxides, oxyhydroxides,
salts, hydrated oxides, carbonates, oxy-carbonates, sulfates,
phosphates, acetates, oxalates and the like. The metal element or
compound comprising the metal element may also be in the form of
any of a number of different polymorphs or crystal structures.
[0172] In certain examples, metal oxides may be hygroscopic and may
change forms once exposed to air, may absorb carbon dioxide, may be
subjected to incomplete calcination or any combination thereof.
Accordingly, although the nanowires are often referred to as metal
oxides, in certain embodiments the nanowires also comprise hydrated
oxides, oxyhydroxides, hydroxides, oxycarbonates (or oxide
carbonates), carbonates or combinations thereof.
[0173] In other embodiments, the nanowires comprise one or more
metal elements from Group 1. In other embodiments, the nanowires
comprise one or more metal elements from Group 2. In other
embodiments, the nanowires comprise one or more metal elements from
Group 3. In other embodiments, the nanowires comprise one or more
metal elements from Group 4. In other embodiments, the nanowires
comprise one or more metal elements from Group 5. In other
embodiments, the nanowires comprise one or more metal elements from
Group 6. In other embodiments, the nanowires comprise one or more
metal elements from Group 7. In other embodiments, the nanowires
comprise one or more metal elements from the lanthanides. In other
embodiments, the nanowires comprise one or more metal elements from
the actinides.
[0174] In one embodiment, the nanowires comprise one or more metal
elements from any of Groups 1-7, lanthanides, actinides or
combinations thereof in the form of an oxide. In another
embodiment, the nanowires comprise one or more metal elements from
Group 1 in the form of an oxide. In another embodiment, the
nanowires comprise one or more metal elements from Group 2 in the
form of an oxide. In another embodiment, the nanowires comprise one
or more metal elements from Group 3 in the form of an oxide. In
another embodiment, the nanowires comprise one or more metal
elements from Group 4 in the form of an oxide. In another
embodiment, the nanowires comprise one or more metal elements from
Group 5 in the form of an oxide. In another embodiment, the
nanowires comprise one or more metal elements from Group 6 in the
form of an oxide. In another embodiment, the nanowires comprise one
or more metal elements from Group 7 in the form of an oxide. In
another embodiment, the nanowires comprise one or more metal
elements from the lanthanides in the form of an oxide. In another
embodiment, the nanowires comprise one or more metal elements from
the actinides in the form of an oxide.
[0175] In other embodiments, the nanowires comprise oxides,
hydroxides, sulfates, carbonates, oxide carbonates, acetates,
oxalates, phosphates (including hydrogenphosphates and
dihydrogenphosphates), oxyhalides, hydroxihalides, oxyhydroxides,
oxysulfates or combinations thereof of one or more metal elements
from any of Groups 1-7, lanthanides, actinides or combinations
thereof. In some other embodiments, the nanowires comprise oxides,
hydroxides, sulfates, carbonates, oxide carbonates, oxalates or
combinations thereof of one or more metal elements from any of
Groups 1-7, lanthanides, actinides or combinations thereof. In
other embodiments, the nanowires comprise oxides, and in other
embodiments, the nanowires comprise hydroxides. In other
embodiments, the nanowires comprise carbonates, and in other
embodiments, the nanowires comprise oxy-carbonates. In other
embodiments, the nanowires comprise Li.sub.2CO.sub.3, LiOH,
Li.sub.2O, Li.sub.2C.sub.2O.sub.4, Li.sub.2SO.sub.4,
Na.sub.2CO.sub.3, NaOH, Na.sub.2O, Na.sub.2C.sub.2O.sub.4,
Na.sub.2SO.sub.4, K.sub.2CO.sub.3, KOH, K.sub.2O,
K.sub.2C.sub.2O.sub.4, K.sub.2SO.sub.4, Cs.sub.2CO.sub.3, CsOH,
Cs.sub.2O, CsC.sub.2O.sub.4, CsSO.sub.4, Be(OH).sub.2, BeCO.sub.3,
BeO, BeC.sub.2O.sub.4. BeSO.sub.4, Mg(OH).sub.2, MgCO.sub.3, MgO,
MgC.sub.2O.sub.4. MgSO.sub.4, Ca(OH).sub.2, CaO, CaCO.sub.3,
CaC.sub.2O.sub.4, CaSO.sub.4, Y.sub.2O.sub.3,
Y.sub.3(CO.sub.3).sub.2, Y(OH).sub.3, Y.sub.2(C.sub.2O4).sub.3,
Y.sub.2(SO4).sub.3, Zr(OH).sub.4, ZrO(OH).sub.2, ZrO2,
Zr(C.sub.2O.sub.4).sub.2, Zr(SO.sub.4).sub.2, Ti(OH).sub.4,
TiO(OH).sub.2, TiO2, Ti(C.sub.2O.sub.4).sub.2, Ti(SO.sub.4).sub.2,
BaO, Ba(OH).sub.2, BaCO.sub.3, BaC.sub.2O.sub.4, BaSO.sub.4,
La(OH).sub.3, La.sub.2O.sub.3, La.sub.2(C.sub.2O.sub.4).sub.3,
La.sub.2(SO.sub.4).sub.3, La.sub.2(CO.sub.3).sub.3, Ce(OH).sub.4,
CeO.sub.2, Ce.sub.2O.sub.3, Ce(C.sub.2O.sub.4).sub.2,
Ce(SO.sub.4).sub.2, Ce(CO.sub.3).sub.2, ThO.sub.2, Th(OH).sub.4,
Th(C.sub.2O.sub.4).sub.2, Th(SO.sub.4).sub.2, Th(CO.sub.3).sub.2,
Sr(OH).sub.2, SrCO.sub.3, SrO, SrC.sub.2O.sub.4, SrSO.sub.4,
Sm.sub.2O.sub.3, Sm(OH).sub.3, Sm.sub.2(CO.sub.3).sub.3,
Sm.sub.2(C.sub.2O.sub.3).sub.3, Sm.sub.2(SO.sub.4).sub.3,
LiCa.sub.2Bi.sub.3O.sub.4Cl.sub.6, NaMnO.sub.4, Na.sub.2WO.sub.4,
NaMn/WO.sub.4, CoWO.sub.4, CuWO.sub.4, K/SrCoO.sub.3,
K/Na/SrCoO.sub.3, Na/SrCoO.sub.3, Li/SrCoO.sub.3, SrCoO.sub.3,
Mg.sub.6MnO.sub.8, LiMn.sub.2O.sub.4, Li/Mg.sub.6MnO.sub.8,
Na.sub.10Mn/W.sub.5O.sub.17, Mg.sub.3Mn.sub.3B.sub.2O.sub.10,
Mg.sub.3(BO.sub.3).sub.2, molybdenum oxides, molybdenum hydroxides,
molybdenum oxalates, molybdenum sulfates, Mn.sub.2O.sub.3,
Mn.sub.3O.sub.4, manganese oxides, manganese hydroxides, manganese
oxalates, manganese sulfates, manganese tungstates, manganese
carbonates, vanadium oxides, vanadium hydroxides, vanadium
oxalates, vanadium sulfates, tungsten oxides, tungsten hydroxides,
tungsten oxalates, tungsten sulfates, neodymium oxides, neodymium
hydroxides, neodymium carbonates, neodymium oxalates, neodymium
sulfates, europium oxides, europium hydroxides, europium
carbonates, europium oxalates, europium sulfates, praseodymium
oxides, praseodymium hydroxides, praseodymium carbonates,
praseodymium oxalates, praseodymium sulfates, rhenium oxides,
rhenium hydroxides, rhenium oxalates, rhenium sulfates, chromium
oxides, chromium hydroxides, chromium oxalates, chromium sulfates,
potassium molybdenum oxides/silicon oxide or combinations
thereof.
[0176] In other embodiments, the nanowires comprise Li.sub.2O,
Na.sub.2O, K.sub.2O, Cs.sub.2O, BeO MgO, CaO, ZrO(OH).sub.2, ZrO2,
TiO.sub.2, TiO(OH).sub.2, BaO, Y.sub.2O.sub.3, La.sub.2O.sub.3,
CeO.sub.2, Ce.sub.2O.sub.3, ThO.sub.2, SrO, Sm.sub.2O.sub.3,
Nd.sub.2O.sub.3, Eu.sub.2O.sub.3, Pr.sub.2O.sub.3,
LiCa.sub.2Bi.sub.3O.sub.4Cl.sub.6, NaMnO.sub.4, Na.sub.2WO.sub.4,
Na/Mn/WO.sub.4, Na/MnWO.sub.4, Mn/WO4, K/SrCoO.sub.3,
K/Na/SrCoO.sub.3, K/SrCoO.sub.3, Na/SrCoO.sub.3, Li/SrCoO.sub.3,
SrCoO.sub.3, Mg.sub.6MnO.sub.8, Na/B/Mg.sub.6MnO.sub.8,
Li/B/Mg.sub.6MnO.sub.8, Zr.sub.2Mo.sub.2O.sub.8, molybdenum oxides,
Mn.sub.2O.sub.3, Mn.sub.3O.sub.4, manganese oxides, vanadium
oxides, tungsten oxides, neodymium oxides, rhenium oxides, chromium
oxides, or combinations thereof.
[0177] In still other aspects, the nanowires comprise lanthanide
containing perovskites. A perovskite is any material with the same
type of crystal structure as calcium titanium oxide (CaTiO.sub.3).
Examples of perovskites within the context of the present
disclosure include, but are not limited to, LaCoO.sub.3 and
La/SrCoO.sub.3.
[0178] In other embodiments, the nanowires comprise TiO.sub.2,
Sm.sub.2O.sub.3, V.sub.2O.sub.5, MoO.sub.3, BeO, MnO.sub.2, MgO,
La.sub.2O.sub.3, Nd.sub.2O.sub.3, Eu.sub.2O.sub.3, ZrO.sub.2, SrO,
Na.sub.2WO.sub.4, Mn/WO.sub.4, BaO, Mn.sub.2O.sub.3,
Mn.sub.3O.sub.4, Mg.sub.6MnO.sub.8, Na/B/Mg.sub.6MnO.sub.8,
Li/B/Mg.sub.6MnO.sub.8, NaMnO.sub.4, CaO or combinations thereof.
In further embodiments, the nanowires comprise MgO,
La.sub.2O.sub.3, Nd.sub.2O.sub.3, Na.sub.2WO.sub.4, Mn/WO.sub.4,
Mn.sub.2O.sub.3, Mn.sub.3O.sub.4, Mg.sub.6MnO.sub.8,
Na/B/Mg.sub.6MnO.sub.8, Li/B/Mg.sub.6MnO.sub.8 or combinations
thereof.
[0179] In some embodiments, the nanowires comprises Mg, Ca, Sr, Ba,
Y, La, W, Mn, Mo, Nd, Sm, Eu, Pr, Zr or combinations thereof, and
in other embodiments the nanowire comprises MgO, CaO, SrO, BaO,
Y.sub.2O.sub.3, La.sub.2O.sub.3, Na.sub.2WO.sub.4, Mn.sub.2O.sub.3,
Mn.sub.3O.sub.4, Nd.sub.2O.sub.3, Sm.sub.2O.sub.3, Eu.sub.2O.sub.3,
Pr.sub.2O.sub.3, Mg.sub.6MnO.sub.8, NaMnO.sub.4, Na/Mn/W/O,
Na/MnWO.sub.4, MnWO.sub.4 or combinations thereof.
[0180] In more specific embodiments, the nanowires comprise MgO. In
other specific embodiments, the nanowires comprise CaO. In other
embodiments, the nanowires comprise SrO. In other specific
embodiments, the nanowires comprise La.sub.2O.sub.3. In other
specific embodiments, the nanowires comprise Na.sub.2WO.sub.4 and
may optionally further comprise Mn/WO.sub.4. In other specific
embodiments, the nanowires comprise Mn.sub.2O.sub.3. In other
specific embodiments, the nanowires comprise Mn.sub.3O.sub.4. In
other specific embodiments, the nanowires comprise
Mg.sub.6MnO.sub.8. In other specific embodiments, the nanowires
comprise NaMnO.sub.4. In other specific embodiments, the nanowires
comprise Nd.sub.2O.sub.3. In other specific embodiments, the
nanowires comprise Eu.sub.2O.sub.3. In other specific embodiments,
the nanowires comprise Pr.sub.2O.sub.3. In some other embodiments,
the nanowires comprise Sm.sub.2O.sub.3.
[0181] In certain embodiments, the nanowires comprise an oxide of a
group 2 element. For example, in some embodiments, the nanowires
comprise an oxide of magnesium. In other embodiments, the nanowires
comprise an oxide of calcium. In other embodiments, the nanowires
comprise an oxide of strontium. In other embodiments, the nanowires
comprise an oxide of barium.
[0182] In certain other embodiments, the nanowires comprise an
oxide of a group 3 element. For example, in some embodiments, the
nanowires comprise an oxide of yttrium. In other embodiments, the
nanowires comprise an oxide of scandium.
[0183] In yet other certain embodiments, the nanowires comprise an
oxide of an early lanthanide element. For example, in some
embodiments, the nanowires comprise an oxide of lanthanum. In other
embodiments, the nanowires comprise an oxide of cerium. In other
embodiments, the nanowires comprise an oxide of praseodymium. In
other embodiments, the nanowires comprise an oxide of neodymium. In
other embodiments, the nanowires comprise an oxide of promethium.
In other embodiments, the nanowires comprise an oxide of samarium.
In other embodiments, the nanowires comprise an oxide of europium.
In other embodiments, the nanowires comprise an oxide of
gadolinium.
[0184] In certain other embodiments, the nanowires comprise a
lanthanide in the form of an oxy-carbonate. For example, the
nanowires may comprise Ln.sub.2O.sub.2(CO.sub.3), where Ln
represents a lanthanide. Examples in this regard include: La, Ce,
Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
oxy-carbonates. In other embodiments, the nanowires comprise an
oxy-carbonate of one or more elements from any of Groups 1 through
7, lanthanides, actinides or combinations thereof. Accordingly in
one embodiment the nanowires comprise Li, Na, K, Rb, Cs, Fr, Be,
Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc
or Re oxy-carbonate. In other embodiments, the nanowires comprise
Ac, Th, U or Pa oxide carbonate. An oxy-carbonate may be
represented by the following formula:
M.sub.xO.sub.y(CO.sub.3).sub.z, wherein M is a metal element from
any of Groups 1 through 7, lanthanides or actinides and x, y and z
are intergers such that the overall charge of the metal
oxy-carbonate is neutral.
[0185] In certain other embodiments, the nanowires comprise a
carbonate of a group 2 element. For example, the nanowires may
comprise MgCO.sub.3, CaCO.sub.3, SrCO.sub.3, BaCO.sub.3 or
combination thereof. In other embodiments, the nanowires comprise a
carbonate of one or more elements from any of the Group 1 through
7, lanthanides and actinides or combination thereof. Accordingly in
one embodiment the nanowires comprise a Li, Na, K, Rb, Cs, Fr, Be,
Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn,
Tc, Re, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,
Ac, Th, Pa or U carbonate.
[0186] In other embodiments, the nanowires comprise TiO.sub.2,
Sm.sub.2O.sub.3, V.sub.2O.sub.5, MoO.sub.3, BeO, MnO.sub.2, MgO,
La.sub.2O.sub.3, ZrO.sub.2, SrO, Na.sub.2WO.sub.4, BaCO.sub.3,
Mn.sub.2O.sub.3, Mn.sub.3O.sub.4, Mg.sub.6MnO.sub.8,
Na/B/Mg.sub.6MnO.sub.8, Li/B/Mg.sub.6MnO.sub.8,
Zr.sub.2Mo.sub.2O.sub.8, NaMnO.sub.4, CaO or combinations thereof
and further comprise one or more dopants comprised of metal
elements, semi-metal elements, non-metal elements or combinations
thereof. In some further embodiments, the nanowires comprise MgO,
La.sub.2O.sub.3, Na.sub.2WO.sub.4, Mn.sub.2O.sub.3,
Mn.sub.3O.sub.4, Mg.sub.6MnO.sub.8, Zr.sub.2Mo.sub.2O.sub.8,
NaMnO.sub.4 or combinations thereof, and the nanowires further
comprise Li, Sr, Zr, Ba, Mn or Mn/WO.sub.4. In some embodiments,
the nanowires or a catalytic material comprising a plurality of the
nanowires comprise a combination of one or more of metal elements
from any of Groups 1-7, lanthanides or actinides and one or more of
metal elements, semi-metal elements or non-metal elements. For
example in one embodiment, the nanowires comprise the combinations
of Li/Mg/O, Ba/Mg/O, Zr/La/O, Ba/La/O, Sr/La/O, Zr/V/P/O,
Mo/V/Sb/O, V.sub.2O.sub.5/Al.sub.2O.sub.3, Mo/V/O, V/Ce/O,
V/Ti/P/O, V.sub.2O.sub.5/TiO.sub.2, V/P/O/TiO.sub.2,
V/P/O/Al.sub.2O.sub.3, V/Mg/O, V.sub.2O.sub.5/ZrO.sub.2, Mo/V/Te/O,
V/Mo/O/Al.sub.2O.sub.3, Ni/V/Sb/O, Co/V/Sb/O, Sn/V/Sb/O, Bi/V/Sb/O,
Mo/V/Te/Nb/O, Mo/V/Nb/O, V.sub.2O.sub.5/MgO/SiO.sub.2, V/Co,
MoO.sub.3/Al.sub.2O.sub.3, Ni/Nb/O, NiO/Al.sub.2O.sub.3,
Ga/Cr/Zr/P/O, MoO.sub.3/Cl/SiO.sub.2/TiO.sub.2, Co/Cr/Sn/W/O,
Cr/Mo/O, MoO.sub.3/Cl/SiO.sub.2/TiO.sub.2, Co/Ca, NiO/MgO,
MoO.sub.3/Al.sub.2O.sub.3, Nb/P/Mo/O, Mo/V/Te/Sb//Nb/O, La/Na/Al/O,
Ni/Ta/Nb/O, Mo/Mn/V/W/O, Li/Dy/Mg/O, Sr/La/Nd/O, Co/Cr/Sn/W/O,
MoO.sub.3/SiO.sub.2/TiO.sub.2, Sm/Na/P/O, Sm/Sr/O, Sr/La/Nd/O,
Co/P/O/TiO.sub.2, La/Sr/Fe/Cl/O, La/Sr/Cu/Cl/O, Y/Ba/Cu/O, Na/Ca/O,
V.sub.2O.sub.5/ZrO.sub.2, V/Mg/O, Mn/V/Cr/W/O/Al.sub.2O.sub.3,
V.sub.2O.sub.5/K/SiO.sub.2, V.sub.2O.sub.5/Ca/TiO.sub.2,
V.sub.2O.sub.5/K/TiO.sub.2, V/Mg/Al/O, V/Zr/O, V/Nb/O,
V.sub.2O.sub.5/Ga.sub.2O.sub.3, V/Mg/Al/O, V/Nb/O, V/Sb/O, V/Mn/O,
V/Nb/O/Sb.sub.2O.sub.4, V/Sb/O/TiO.sub.2, V.sub.2O.sub.5/Ca,
V.sub.2O.sub.5/K/Al.sub.2O.sub.3, V.sub.2O.sub.5/TiO.sub.2,
V.sub.2O.sub.5/MgO/TiO.sub.2, V.sub.2O.sub.5/ZrO.sub.2, V/Al/F/O,
V/Nb/O/TiO.sub.2, Ni/V/O, V.sub.2O.sub.5/SmVO.sub.4, V/W/O,
V.sub.2O.sub.5/Zn/Al.sub.2O.sub.3, V.sub.2O.sub.5/CeO.sub.2,
V/Sm/O, V.sub.2O.sub.5/TiO.sub.2/SiO.sub.2,
Mo/Li/O/Al.sub.2O.sub.3, Mg/Dy/Li/Cl/O, Mg/Dy/Li/Cl/O, Ce/Ni/O,
Ni/Mo/O/V, Ni/Mo/O/V/N, Ni/Mo/O Sb/O/N,
MoO.sub.3/Cl/SiO.sub.2/TiO.sub.2, Co/Mo/O, Ni/Ti/O, Ni/Zr/O, Cr/O,
MoO.sub.3/Al.sub.2O.sub.3, Mn/P/O, MoO.sub.3/K/ZrO.sub.2, Na/W/O,
Mn/Na/W/O, Mn/Na//W/O/SiO.sub.2, Na/W/O/SiO.sub.2, Mn/Mo/O,
Nb.sub.2O.sub.5/TiO.sub.2, Co/W/O, Ni/Mo/O, Ga/Mo/O, Mg/Mo/V/O,
Cr.sub.2O.sub.3/Al.sub.2O.sub.3, Cr/Mo/Cs/O/Al.sub.2O.sub.3,
Co/Sr/O/Ca, Ag/Mo/P/O, MoO.sub.3/SmVO.sub.4, Mo/Mg/Al/O,
MoO.sub.3/K/SiO.sub.2/TiO.sub.2, Cr/Mo/O/Al.sub.2O.sub.3,
MoO.sub.3/Al.sub.2O.sub.3, Ni/Co/Mo/O, Y/Zr/O, Y/Hf, Zr/Mo/Mn/O,
Mg/Mn/O, Li/Mn/O, Mg/Mn/B/O, Mg/B/O, Na/B/Mg/Mn/O, Li/B/Mg/Mn/O,
Mn/Na/P/O, Na/Mn/Mg/O, Zr/Mo/O, Mn/W/O or Mg/Mn/O.
[0187] In a specific embodiment, the nanowires comprise the
combinations of Li/Mg/O, Ba/Mg/O, Zr/La/O, Ba/La/O, Sr/La/O,
Sr/Nd/O, La/O, Nd/O, Eu/O, Mg/La/O, Mg/Nd/O, Na/La/O, Na/Nd/O,
Sm/O, Mn/Na/W/O, Mg/Mn/O, Na/B/Mg/Mn/O, Li/B/Mg/Mn/O, Zr/Mo/O or
Na/Mn/Mg/O. For example, in some embodiments the nanowires comprise
the combinations of Li/MgO, Ba/MgO, Sr/La.sub.2O.sub.3,
Ba/La.sub.2O.sub.3, Mn/Na.sub.2WO.sub.4,
Mn/Na.sub.2WO.sub.4/SiO.sub.2, Mn.sub.2O.sub.3/Na.sub.2WO.sub.4,
Mn.sub.3O.sub.4/Na.sub.2WO.sub.4, Li/B/Mg.sub.6MnO.sub.8,
Na/B/Mg.sub.6MnO.sub.8 or NaMnO.sub.4/MgO. In certain embodiments,
the nanowire comprises Li/MgO, Ba/MgO, Sr/La.sub.2O.sub.3,
Mg/Na/La.sub.2O.sub.3, Sr/Nd.sub.2O.sub.3, or
Mn/Na.sub.2WO.sub.4.
[0188] In some other specific embodiments, the nanowires comprise
the combination of Li/MgO. In other specific embodiments, the
nanowires comprise the combination of Ba/MgO. In other specific
embodiments, the nanowires comprise the combination of
Sr/La.sub.2O.sub.3. In other specific embodiments, the nanowires
comprise the combination of Ba/La.sub.2O.sub.3. In other specific
embodiments, the nanowires comprise the combination of
Mn/Na.sub.2WO.sub.4. In other specific embodiments, the nanowires
comprise the combination of Mn/Na.sub.2WO.sub.4/SiO.sub.2. In other
specific embodiments, the nanowires comprise the combination of
Mn.sub.2O.sub.3/Na.sub.2WO.sub.4. In other specific embodiments,
the nanowires comprise the combination of
Mn.sub.3O.sub.4/Na.sub.2WO.sub.4. In other specific embodiments,
the nanowires comprise the combination of
Mn/WO.sub.4/Na.sub.2WO.sub.4. In other specific embodiments, the
nanowires comprise the combination of Li/B/Mg.sub.6MnO.sub.8. In
other specific embodiments, the nanowires comprise the combination
of Na/B/Mg.sub.6MnO.sub.8. In other specific embodiments, the
nanowires comprise the combination of NaMnO.sub.4/MgO.
[0189] Polyoxyometalates (POM) are a class of metal oxides that
range in structure from the molecular to the micrometer scale. The
unique physical and chemical properties of POM clusters, and the
ability to tune these properties by synthetic means have attracted
significant interest from the scientific community to create
"designer" materials. For example, heteropolyanions such as the
well-known Keggin [XM.sub.12O.sub.40].sup.- and Wells-Dawson
[X.sub.2M1.sub.8O.sub.62].sup.- anions (where M=W or Mo; and X=a
tetrahedral template such as but not limited to Si, Ge, P) and
isopolyanions with metal oxide frameworks with general formulas
[MO.sub.x].sub.n where M=Mo, W, V, and Nb and x=4-7 are ideal
candidates for OCM/ODH catalysts. Accordingly, in one embodiment
the nanowires comprise [XM.sub.12O.sub.40].sup.- or
[X.sub.2M1.sub.8O.sub.62].sup.- anions (where M=W or Mo; and X=a
tetrahedral template such as but not limited to Si, Ge, P) and
isopolyanions with metal oxide frameworks with general formulas
[MO.sub.x].sub.n where M=Mo, W, V, and Nb and x=4-7. In some
embodiments, X is P or Si.
[0190] These POM clusters have "lacunary" sites that can
accommodate divalent and trivalent first row transition metals, the
metal oxide clusters acting as ligands. These lacunary sites are
essentially "doping" sites, allowing the dopant to be dispersed at
the molecular level instead of in the bulk which can create pockets
of unevenly dispersed doped material. Because the POM clusters can
be manipulated by standard synthetic techniques, POMs are highly
modular and a wide library of materials can be prepared with
different compositions, cluster size, and dopant oxidation state.
These parameters can be tuned to yield desired OCM/ODH catalytic
properties. Accordingly, one embodiment of the present disclosure
is a nanowire comprising one or more POM clusters. Such nanowires
find utility as catalysts, for example, in the OCM and ODH
reactions.
[0191] Silica doped sodium manganese tungstate
(NaMn/WO.sub.4/SiO.sub.2) is a promising OCM catalyst. The
NaMn/WO.sub.4/SiO.sub.2 system is attractive due to its high C2
selectivity and yield. Unfortunately, good catalytic activity is
only achievable at temperatures greater than 800.degree. C. and
although the exact active portion of the catalyst is still subject
to debate, it is thought that sodium plays an important role in the
catalytic cycle. In addition, the NaMn/WO.sub.4/SiO.sub.2 catalyst
surface area is relatively low <2 m.sup.2/g. Manganese tungstate
(Mn/WO.sub.4) nanorods (i.e., straight nanowires) can be used to
model a NaMn/WO.sub.4/SiO.sub.2 based nanowire OCM catalyst. The
Mn/WO.sub.4 nanorods are prepared hydro-thermally and the size can
be tuned based on reaction conditions with dimensions of 25-75 nm
in diameter to 200-800 nm in length. The as-prepared nano-rods have
higher surface areas than the NaMn/WO.sub.4/SiO.sub.2 catalyst
systems. In addition, the amount of sodium, or other elements, can
be precisely doped into the Mn/WO.sub.4 nanorod material to target
optimal catalytic activity. Nanorod tungstate based materials can
be expanded to, but not limited to, CoWO.sub.4 or CuWO.sub.4
materials, which may serve as base materials for OCM/ODH catalysis.
In addition to straight nanowires, the above discussion applies to
the disclosed nanowires having a bent morphology as well. The
nanowires of the disclosure may be analyzed by inductively coupled
plasma mass spectrometry (ICP-MS) to determine the element content
of the nanowires. ICP-MS is a type of mass spectrometry that is
highly sensitive and capable of the determination of a range of
metals and several non-metals at concentrations below one part in
10.sup.12. ICP is based on coupling together an inductively coupled
plasma as a method of producing ions (ionization) with a mass
spectrometer as a method of separating and detecting the ions.
ICP-MS methods are well known in the art.
[0192] In some embodiments, the nanowire comprises a combination of
two or more metal compounds, for example metal oxides. For example,
in some embodiments, the nanowire comprises
Mn.sub.2O.sub.3/Na.sub.2WO.sub.4,
Mn.sub.3O.sub.4/Na.sub.2WO.sub.4MnWO.sub.4/Na.sub.2WO.sub.4/Mn.sub.2O.sub-
.3, MnWO.sub.4/Na.sub.2WO.sub.4/Mn.sub.3O.sub.4 or
NaMnO.sub.4/MgO.
[0193] Certain rare earth compositions have been found to be useful
catalysts, for example as catalysts in the OCM reaction. Thus, in
one embodiment, the nanowire catalysts comprise lanthanide oxides
such as La.sub.2O.sub.3, Nd.sub.2O.sub.3, Yb.sub.2O.sub.3,
Eu.sub.2O.sub.3 or Sm.sub.2O.sub.3. In other embodiments, the
nanowires comprise mixed oxides of lanthanide metals. Such mixed
oxides are represented by Ln1.sub.4-xLn2.sub.xO.sub.6, wherein Ln1
and Ln2 are each independently a lanthanide element and x is a
number ranging from greater than 0 to less than 4. In other more
specific embodiments, the lanthanide mixed oxides comprise
La.sub.4-xLn1.sub.xO.sub.6, wherein Ln1 is a lanthanide element and
x is a number ranging from greater than 0 to less than 4. For
example, in some embodiments the lanthanide mixed oxides are mixed
oxides of lanthanum and neodymium and the nanowires comprise
La.sub.4-xNd.sub.xO.sub.6, wherein x is a number ranging from
greater than 0 to less than 4 have also been found to be useful in
the OCM reaction. For example La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6,
La.sub.1.5Nd.sub.2.5O.sub.6, La.sub.2.5Nd.sub.1.5O.sub.6,
La.sub.3.2Nd.sub.0.8O.sub.6, La.sub.3.5Nd.sub.0.5O.sub.6,
La.sub.3.8Nd.sub.0.2O.sub.6, or combinations thereof have been
found to be useful OCM catalyst compositions.
[0194] Any of the foregoing nanowire catalysts may have any
morphology (e.g., bent, straight, etc.) and may be prepared via any
method described herein or known in the art. For example, these
nanowires may be prepared from any of the polymer templates
described herein or known in the art. Also as discussed below,
certain dopant combinations with the above lanthanide nanowires
have been found to be useful for enhancing the catalytic activity
of the nanowires.
[0195] In other embodiments the nanowires are in a core/shell
arrangement (see below) and the nanowires comprise Eu on a MgO
core; La on a MgO core; Nd on a MgO core; Sm on a MgO core; Y--Ce
on a Na doped MgO core Na or Na doped Ce--Y on a MgO core.
[0196] In an aspect of the invention, nanowires, and materials
comprising the same, having the empirical formula
M4.sub.wM5.sub.xM6.sub.yO, are provided, wherein each M4 is
independently one or more elements selected from Groups 1 through
4, each M5 is independently one or more elements selected from
Group 7 and M6 is independently one or more elements selected from
Groups 5 through 8 and Groups 14 through 15 and w, x, y and z are
integers such that the overall charge is balanced.
[0197] In some embodiments, M4 comprises one or more elements
selected from Group 1, such as sodium (Na), while M6 includes one
or more elements selected from Group 6, such as tungsten (W) and M5
is Mn. In another embodiment, M4 is Na, M5 is Mn, M6 is W, the
ratio of w:x is 10:1, and the ratio of w:y is 2:1. In such a case,
the overall empirical formula of the nanowire is
Na.sub.10MnW.sub.5O.sub.z. When Na is in the +1 oxidation state, W
is in the +6 oxidation state, and Mn is in the +4 oxidation state,
z must equal 17 so as to fill the valence requirements of Na, W and
Mn. As a result, the overall empirical formula of the nanowire in
this embodiment is Na.sub.10MnW.sub.5O.sub.17.
[0198] In other embodiments, the ratios of w:x can be 1:1, or 5:1,
or 15:1, or 25:1, or 50:1. In yet other embodiments, for any given
ratio of w:x, the ratios of w:y can be 1:5, or 1:2, or 1:2, or 5:1.
In still other embodiments, any nanowire of the empirical formula
M4.sub.wM5.sub.xM6.sub.yO.sub.z, including the nanowire of the
empirical formula M4.sub.10MnM6.sub.5O.sub.17 described above, can
be supported on an oxide substrate. Oxide substrates can include
silica, alumina, and titania. The reaction that anchors nanowire
materials onto oxide substrates is analogous to the reaction that
anchors bulk materials onto oxide substrates, such as that
described in U.S. Pat. No. 4,808,563, which is entirely
incorporated herein by reference. Alternatively, non-oxide support,
for example silicon carbide can be used to support nanowires of the
present invention, for example Na.sub.10MnW.sub.5O.sub.17 nanowires
and others. Silicon carbide has very good high temperature
stability and chemical inertness toward OCM reaction intermediates
and thus is particularly effective as a support in this
reaction.
[0199] 3. Catalytic Materials
[0200] As noted above, the present disclosure provides a catalytic
material comprising a plurality of nanowires. In certain
embodiments, the catalytic material comprises a support or carrier.
The support is preferably porous and has a high surface area. In
some embodiments the support is active (i.e. has catalytic
activity). In other embodiments, the support is inactive (i.e.
non-catalytic). In some embodiments, the support comprises an
inorganic oxide, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, MgO, CaO,
SrO, ZrO.sub.2, ZnO, LiAlO.sub.2, MgAl.sub.2O.sub.4, MnO,
MnO.sub.2, Mn.sub.3O.sub.4, La.sub.2O.sub.3, AlPO4,
SiO.sub.2/Al.sub.2O.sub.3, activated carbon, silica gel, zeolites,
activated clays, activated Al.sub.2O.sub.3, SiC, diatomaceous
earth, magnesia, aluminosilicates, calcium aluminate, support
nanowires or combinations thereof. In some embodiments the support
comprises silicon, for example SiO.sub.2. In other embodiments the
support comprises magnesium, for example MgO. In other embodiments
the support comprises zirconium, for example ZrO.sub.2. In yet
other embodiments, the support comprises lanthanum, for example
La.sub.2O.sub.3. In yet other embodiments, the support comprises
lanthanum, for example Y.sub.2O.sub.3. In yet other embodiments,
the support comprises hafnium, for example HfO.sub.2. In yet other
embodiments, the support comprises aluminum, for example
Al.sub.2O.sub.3. In yet other embodiments, the support comprises
gallium, for example Ga.sub.2O.sub.3.
[0201] In still other embodiments, the support material comprises
an inorganic oxide, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, MgO,
ZrO.sub.2, HfO2, CaO, SrO, ZnO, LiAlO.sub.2, MgAl.sub.2O.sub.4,
MnO, MnO.sub.2, Mn.sub.2O.sub.4, Mn.sub.3O.sub.4, La.sub.2O.sub.3,
activated carbon, silica gel, zeolites, activated clays, activated
Al.sub.2O.sub.3, diatomaceous earth, magnesia, aluminosilicates,
calcium aluminate, support nanowires or combinations thereof. For
example, the support material may comprise SiO.sub.2, ZrO.sub.2,
CaO, La.sub.2O.sub.3 or MgO.
[0202] In still other embodiments, the support material comprises a
carbonate. For example, in some embodiments the support material
comprises MgCO.sub.3, CaCO.sub.3, SrCO.sub.3, BaCO.sub.3,
Y.sub.2(CO.sub.3).sub.3, La.sub.2(CO.sub.3).sub.3 or combinations
thereof.
[0203] In yet other embodiments, a nanowire may serve as a support
for another nanowire. For example, a nanowire may be comprised of
non-catalytic metal elements and adhered to or incorporated within
the support nanowire is a catalytic nanowire. For example, in some
embodiments, the support nanowires are comprised of SiO.sub.2, MgO,
CaO, SrO, TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3, ZnO MgCO.sub.3,
CaCO.sub.3, SrCO.sub.3 or combinations thereof. Preparation of
nanowire supported nanowire catalysts (i.e., core/shell nanowires)
is discussed in more detail below. The optimum amount of nanowire
present on the support depends, inter alia, on the catalytic
activity of the nanowire. In some embodiments, the amount of
nanowire present on the support ranges from 1 to 100 parts by
weight nanowires per 100 parts by weight of support or from 10 to
50 parts by weight nanowires per 100 parts by weight of support. In
other embodiments, the amount of nanowire present on the support
ranges from 100-200 parts of nanowires per 100 parts by weight of
support, or 200-500 parts of nanowires per 100 parts by weight of
support, or 500-1000 parts of nanowires per 100 parts by weight of
support. Typically, heterogeneous catalysts are used either in
their pure form or blended with inert materials, such as silica,
alumina, etc. The blending with inert materials is used in order to
reduce and/or control large temperature non-uniformities within the
reactor bed often observed in the case of strongly exothermic (or
endothermic) reactions. In the case of complex multistep reactions,
such as the reaction to convert methane into ethylene (OCM),
typical blending materials can selectively slow down or quench one
or more of the reactions of the system and promote unwanted side
reactions. For example, in the case of the oxidative coupling of
methane, silica and alumina can quench the methyl radicals and thus
prevent the formation of ethane. In certain aspects, the present
disclosure provides a catalytic material which solves these
problems typically associated with catalyst support material.
Accordingly, in certain embodiments the catalytic activity of the
catalytic material can be tuned by blending two or more catalysts
and/or catalyst support materials. The blended catalytic material
may comprise a catalytic nanowire as described herein and a bulk
catalyst material and/or inert support material.
[0204] The blended catalytic materials comprise metal oxides,
hydroxides, oxy-hydroxides, carbonates, oxalates of the groups
1-16, lanthanides, actinides or combinations thereof. For example,
the blended catalytic materials may comprise a plurality of
inorganic catalytic polycrystalline nanowires, as disclosed herein,
and any one or more of straight nanowires, nanoparticles, bulk
materials and inert support materials. Methods for preparing such
other materials (e.g., straight nanowires) are known in the art and
described in co-pending U.S. application Ser. No. 13/115,082, which
application is hereby incorporated by reference in its entirety.
Bulk materials are defined as any material in which no attempt to
control the size and/or morphology was performed during its
synthesis. The catalytic materials may be undoped or may be doped
with any of the dopants described herein.
[0205] In one embodiment, the catalyst blend comprises at least one
type 1 component and at least one type 2 component. Type 1
components comprise catalysts having a high OCM activity at
moderately low temperatures and type 2 components comprise
catalysts having limited or no OCM activity at these moderately low
temperatures, but are OCM active at higher temperatures. For
example, in some embodiments the type 1 component is a catalyst
(e.g., nanowire) having high OCM activity at moderately low
temperatures. For example, the type 1 component may comprise a C2
yield of greater than 5% or greater than 10% at temperatures less
than 800.degree. C., less than 700.degree. C. or less than
600.degree. C. The type 2 component may comprise a C2 yield less
than 0.1%, less than 1% or less than 5% at temperatures less than
800.degree. C., less than 700.degree. C. or less than 600.degree.
C. The type 2 component may comprise a C2 yield of greater than
0.1%, greater than 1%, greater than 5% or greater than 10% at
temperatures greater than 800.degree. C., greater than 700.degree.
C. or greater than 600.degree. C. Typical type 1 components include
nanowires, for example polycrystalline nanowires as described
herein, while typical type 2 components include bulk OCM catalysts
and nanowire catalysts which only have good OCM activity at higher
temperatures, for example greater than 800.degree. C. Examples of
type 2 components may include catalysts comprising MgO. The
catalyst blend may further comprise inert support materials as
described above (e.g., silica, alumina, silicon carbide, etc.).
[0206] In certain embodiments, the type 2 component acts as diluent
in the same way an inert material does and thus helps reduce and/or
control hot spots in the catalyst bed caused by the exothermic
nature of the OCM reaction. However, because the type 2 component
is an OCM catalyst, albeit not a particularly active one, it may
prevent the occurrence of undesired side reactions, e.g. methyl
radical quenching. Additionally, controlling the hotspots has the
beneficial effect of extending the lifetime of the catalyst.
[0207] For example, it has been found that diluting active
lanthanide oxide OCM catalysts (e.g., nanowires) with as much as a
10:1 ratio of MgO, which by itself is not an active OCM catalyst at
the temperature which the lanthanide oxide operates, is a good way
to minimize "hot spots" in the reactor catalyst bed, while
maintaining the selectivity and yield performance of the catalyst.
On the other hand, doing the same dilution with quartz SiO.sub.2 is
not effective because it appears to quench the methyl radicals
which serve to lower the selectivity to C2s.
[0208] In yet another embodiment, the type 2 components are good
oxidative dehydrogenation (ODH) catalysts at the same temperature
that the type 1 components are good OCM catalysts. In this
embodiment, the ethylene/ethane ratio of the resulting gas mixture
can be tuned in favor of higher ethylene. In another embodiment,
the type 2 components are not only good ODH catalysts at the same
temperature the type 1 components are good OCM catalysts, but also
have limited to moderate OCM activity at these temperatures.
[0209] In related embodiments, the catalytic performance of the
catalytic material is tuned by selecting specific type 1 and type 2
components of a catalyst blend. In another embodiment, the
catalytic performance is tuned by adjusting the ratio of the type 1
and type 2 components in the catalytic material. For example, the
type 1 catalyst may be a catalyst for a specific step in the
catalytic reaction, while the type 2 catalyst may be specific for a
different step in the catalytic reaction. For example, the type 1
catalyst may be optimized for formation of methyl radicals and the
type 2 catalyst may be optimized for formation of ethane or
ethylene.
[0210] In other embodiments, the catalytic material comprises at
least two different components (component 1, component 2, component
3, etc.). The different components may comprise different
morphologies, e.g. nanowires, nanoparticles, bulk, etc. The
different components in the catalyst material can be, but not
necessarily, of the same chemical composition and the only
difference is in the morphology and/or the size of the particles.
This difference in morphology and particle size may result in a
difference in reactivity at a specific temperature. Additionally,
the difference in morphology and particle size of the catalytic
material components is advantageous for creating a very intimate
blending, e.g. very dense packing of the catalysts particles, which
can have a beneficial effect on catalyst performance. Also, the
difference in morphology and particle size of the blend components
would allow for control and tuning of the macro-pore distribution
in the reactor bed and thus its catalytic efficiency. An additional
level of micro-pore tuning can be attained by blending catalysts
with different chemical composition and different morphology and/or
particle size. The proximity effect would be advantageous for the
reaction selectivity.
[0211] Accordingly, in one embodiment the present disclosure
provides the use of a catalytic material comprising a first
catalytic nanowire and a bulk catalyst and/or a second catalytic
nanowire in a catalytic reaction, for example the catalytic
reaction may be OCM or ODH. In other embodiments, the first
catalytic nanowire and the bulk catalyst and/or second catalytic
nanowire are each catalytic with respect to the same reaction, and
in other examples the first catalytic nanowire and the bulk
catalyst and/or second catalytic nanowire have the same chemical
composition.
[0212] In some specific embodiments of the foregoing, the catalytic
material comprises a first catalytic nanowire and a second
catalytic nanowire. Each nanowire can have completely different
chemical compositions or they may have the same base composition
and differ only by the doping elements. In other embodiments, each
nanowire can have the same or a different morphology. For example,
each nanowire can differ by the nanowire size (length and/or aspect
ratio), by ratio of actual/effective length, by chemical
composition or any combination thereof. Furthermore, the first and
second nanowires may each be catalytic with respect to the same
reaction but may have different activity. Alternatively, each
nanowire may catalyze different reactions.
[0213] In a related embodiment, the catalytic material comprises a
first catalytic nanowire and a bulk catalyst. The first nanowire
and the bulk catalyst can have completely different chemical
compositions or they may have the same base composition and differ
only by the doping elements. Furthermore, the first nanowire and
the bulk catalyst may each be catalytic with resepect to the same
reaction but may have different activity. Alternatively, the first
nanowire and the bulk catalyst may catalyze different
reactions.
[0214] In yet other embodiments of the foregoing, the catalytic
nanowire has a catalytic activity in the catalytic reaction, which
is greater than a catalytic activity of the bulk catalyst in the
catalytic reaction at the same temperature. In still other
embodiments, the catalytic activity of the bulk catalyst in the
catalytic reaction increases with increasing temperature.
[0215] OCM catalysts may be prone to hotspots due to the very
exothermic nature of the OCM reaction. Diluting such catalysts
helps to manage the hotspots. However, the diluent needs to be
carefully chosen so that the overall performance of the catalyst is
not degraded. Silicon carbide for example can be used as a diluent
with little impact on the OCM selectivity of the blended catalytic
material whereas using silica as a diluent significantly reduces
OCM selectivity. The good heat conductivity of SiC is also
beneficial in minimizing hot spots. As noted above, use of a
catalyst diluents or support material that is itself OCM active has
significant advantages over more traditional diluents such as
silica and alumina, which can quench methyl radicals and thus
reduce the OCM performance of the catalyst. An OCM active diluent
is not expected to have any adverse impact on the generation and
lifetime of methyl radicals and thus the dilution should not have
any adverse impact on the catalyst performance. Thus embodiments of
the invention include catalyst compositions comprising an OCM
catalyst (e.g., any of the disclosed nanowire catalysts) in
combination with a diluent or support material that is also OCM
active. Methods for use of the same in an OCM reaction are also
provided.
[0216] In some embodiments, the above diluent comprises alkaline
earth metal compounds, for example alkaline metal oxides,
carbonates, sulfates or phosphates. Examples of diluents useful in
various embodiments include, but are not limited to, MgO,
MgCO.sub.3, MgSO.sub.4, Mg.sub.3(PO.sub.4).sub.2,
MgAl.sub.2O.sub.4, CaO, CaCO.sub.3, CaSO.sub.4,
Ca.sub.3(PO.sub.4).sub.2, CaAl.sub.2O.sub.4, SrO, SrCO.sub.3,
SrSO.sub.4, Sr.sub.3(PO.sub.4).sub.2, SrAl.sub.2O.sub.4, BaO,
BaCO.sub.3, BaSO.sub.4, Ba.sub.3(PO.sub.4).sub.2, BaAl.sub.2O.sub.4
and the like. Most of these compounds are very cheap, especially
MgO, CaO, MgCO.sub.3, CaCO.sub.3, SrO, SrCO.sub.3 and thus very
attractive for use as diluents from an economic point of view.
Additionally, the magnesium, calcium and strontium compounds are
environmentally friendly too. Accordingly, an embodiment of the
invention provides a catalytic material comprising a catalytic
nanowire in combination with a diluent selected from one or more of
MgO, MgCO.sub.3, MgSO.sub.4, Mg.sub.3(PO.sub.4).sub.2, CaO,
CaCO.sub.3, CaSO.sub.4, Ca.sub.3(PO.sub.4).sub.2, SrO, SrCO.sub.3,
SrSO.sub.4, Sr.sub.3(PO.sub.4).sub.2, BaO, BaCO.sub.3, BaSO.sub.4,
Ba.sub.3(PO.sub.4).sub.2. In some specific embodiments the diluents
is MgO, CaO, SrO, MgCO.sub.3, CaCO.sub.3, SrCO.sub.3 or combination
thereof. Methods for use of the foregoing catalytic materials in an
OCM reaction are also provided. The methods comprise converting
methane to ethane and or ethylene in the presence of the catalytic
materials.
[0217] The above diluents and supports may be employed in any
number of methods. For example, in some embodiments a support
(e.g., MgO, CaO, CaCO.sub.3, SrCO.sub.3) may be used in the form of
a pellet or monolith (e.g., honeycomb) structure, and the nanowire
catalysts may be impregnated or supported thereon. In other
embodiments, a core/shell arrangement is provided and the support
material may form part of the core or shell. For example, a core of
MgO, CaO, CaCO.sub.3 or SrCO.sub.3 may be coated with a shell of
any of the disclosed nanowire compositions.
[0218] In some embodiments, the diluent has a morphology selected
from bulk (e.g. commercial grade), nano (nanowires, nanorods,
nanoparticles, etc.) or combinations thereof.
[0219] In some embodiments, the diluent has none to moderate
catalytic activity at the temperature the OCM catalyst is operated.
In some other embodiments, the diluent has moderate to large
catalytic activity at a temperature higher than the temperature the
OCM catalyst is operated. In yet some other embodiments, the
diluent has none to moderate catalytic activity at the temperature
the OCM catalyst is operated and moderate to large catalytic
activity at temperatures higher than the temperature the OCM
catalyst is operated. Typical temperatures for operating an OCM
reaction according to the present disclosure are 800.degree. C. or
lower, 750.degree. C. or lower, 700.degree. C. or lower,
650.degree. C. or lower, 600.degree. C. or lower and 550.degree. C.
or lower.
[0220] For example, CaCO.sub.3 is a relatively good OCM catalyst at
T>750.degree. C. (50% selectivity, >20% conversion) but has
essentially no activity below 700.degree. C. Experiments performed
in support of the present invention showed that dilution of
Nd.sub.2O.sub.3 straight nanowires with CaCO.sub.3 or SrCO.sub.3
(bulk) showed no degradation of OCM performance and, in some cases,
even better performance than the neat catalyst.
[0221] In some embodiments, the diluent portion in the
catalyst/diluent mixture is 0.01%, 10%, 30%, 50%, 70%, 90% or
99.99% (weight percent) or any other value between 0.01% and 99.9%.
In some embodiments, the dilution is performed with the OCM
catalyst ready to go, e.g. after calcination. In some other
embodiments, the dilution is performed prior to the final
calcination of the catalyst, i.e. the catalyst and the diluent are
calcined together. In yet some other embodiments, the dilution can
be done during the synthesis as well, so that, for example, a mixed
oxide is formed.
[0222] In some embodiments, the catalyst/diluent mixture comprises
more than one catalyst and/or more than one diluent. In some other
embodiments, the catalyst/diluent mixture is pelletized and sized,
or made into shaped extrudates or deposited on a monolith or foam,
or is used as it is. Methods of the invention include taking
advantage of the very exothermic nature of OCM by diluting the
catalyst with another catalyst that is (almost) inactive in the OCM
reaction at the operating temperature of the first catalyst but
active at higher temperature. In these methods, the heat generated
by the hotspots of the first catalyst will provide the necessary
heat for the second catalyst to become active.
[0223] For ease of illustration, the above description of catalytic
materials often refers to OCM; however, such catalytic materials
find utility in other catalytic reactions including but not limited
to: oxidative dehydrogenation (ODH) of alkanes to their
corresponding alkenes, selective oxidation of alkanes and alkenes
and alkynes, oxidation of co, dry reforming of methane, selective
oxidation of aromatics, Fischer-Tropsch, combustion of
hydrocarbons, etc.
[0224] 4. Preparation of Catalytic Materials
[0225] The catalytic materials can be prepared according to any
number of methods known in the art. For example, the catalytic
materials can be prepared after preparation of the individual
components by mixing the individual components in their dry form,
e.g. blend of powders, and optionally, ball milling can be used to
reduce particle size and/or increase mixing. Each component can be
added together or one after the other to form layered particles.
Alternatively, the individual components can be mixed prior to
calcination, after calcination or by mixing already calcined
components with uncalcined components. The catalytic materials may
also be prepared by mixing the individual components in their dry
form and optionally pressing them together into a "pill" followed
by calcination to above 400.degree. C.
[0226] In other examples, the catalytic materials are prepared by
mixing the individual components with one or more solvents into a
suspension or slurry, and optional mixing and/or ball milling can
be used to maximize uniformity and reduce particle size. Examples
of slurry solvents useful in this context include, but are not
limited to: water, alcohols, ethers, carboxylic acids, ketones,
esters, amides, aldehydes, amines, alkanes, alkenes, alkynes,
aromatics, etc. In other embodiments, the individual components are
deposited on a supporting material such as silica, alumina,
magnesia, activated carbon, and the like, or by mixing the
individual components using a fluidized bed granulator.
Combinations of any of the above methods may also be used.
[0227] The catalytic materials may optionally comprise a dopant as
described in more detail below. In this respect, doping material(s)
may be added during preparation of the individual components, after
preparation of the individual components but before drying of the
same, after the drying step but before calcinations or after
calcination. If more than one doping material is used, each dopant
can be added together or one after the other to form layers of
dopants.
[0228] Doping material(s) may also be added as dry components and
optionally ball milling can be used to increase mixing. In other
embodiments, doping material(s) are added as a liquid (e.g.
solution, suspension, slurry, etc.) to the dry individual catalyst
components or to the blended catalytic material. The amount of
liquid may optionally be adjusted for optimum wetting of the
catalyst, which can result in optimum coverage of catalyst
particles by doping material. Mixing and/or ball milling can also
be used to maximize doping coverage and uniform distribution.
Alternatively, doping material(s) are added as a liquid (e.g.
solution, suspension, slurry, etc.) to a suspension or slurry of
the catalyst in a solvent. Mixing and/or ball milling can be used
to maximize doping coverage and uniform distribution. Incorporation
of dopants can also be achieved using any of the methods described
elsewhere herein.
[0229] As noted below, an optional calcination step usually follows
an optional drying step at T<200 C (typically 60-120 C) in a
regular oven or in a vacuum oven. Calcination may be performed on
the individual components of the catalytic material or on the
blended catalytic material. Calcination is generally performed in
an oven/furnace at a temperature higher than the minimum
temperature at which at least one of the components decomposes or
undergoes a phase transformation and can be performed in inert
atmosphere (e.g. N.sub.2, Ar, He, etc.), oxidizing atmosphere (air,
O.sub.2, etc.) or reducing atmosphere (H.sub.2, H.sub.2/N.sub.2,
H.sub.2/Ar, etc.). The atmosphere may be a static atmosphere or a
gas flow and may be performed at ambient pressure, at p<1 atm,
in vacuum or at p>1 atm. High pressure treatment (at any
temperature) may also be used to induce phase transformation
including amorphous to crystalline. Calcinations may also be
performed using microwave heating.
[0230] Calcination is generally performed in any combination of
steps comprising ramp up, dwell and ramp down. For example, ramp to
500.degree. C., dwell at 500.degree. C. for 5 h, ramp down to RT.
Another example includes ramp to 100.degree. C., dwell at
100.degree. C. for 2 h, ramp to 300.degree. C., dwell at
300.degree. C. for 4 h, ramp to 550.degree. C., dwell at
550.degree. C. for 4 h, ramp down to RT. Calcination conditions
(pressure, atmosphere type, etc.) can be changed during the
calcination. In some embodiments, calcination is performed before
preparation of the blended catalytic material (i.e., individual
components are calcined), after preparation of the blended
catalytic material but before doping, after doping of the
individual components or blended catalytic material. Calcination
may also be performed multiple times, e.g. after catalyst
preparation and after doping.
[0231] The catalytic materials may be incorporated into a reactor
bed for performing any number of catalytic reactions (e.g., OCM,
ODH and the like). Accordingly, in one embodiment the present
disclosure provides a catalytic material as disclosed herein in
contact with a reactor and/or in a reactor bed. For example, the
reactor may be for performing an OCM reaction, may be a fixed bed
reactor and may have a diameter greater than 1 inch. In this
regard, the catalytic material may be packed neat (without
diluents) or diluted with an inert material (e.g., sand, silica,
alumina, etc.) The catalyst components may be packed uniformly
forming a homogeneous reactor bed.
[0232] The particle size of the individual components within a
catalytic material may also alter the catalytic activity, and other
properties, of the same. Accordingly, in one embodiment, the
catalyst is milled to a target average particle size or the
catalyst powder is sieved to select a particular particle size. In
some aspects, the catalyst powder may be pressed into pellets and
the catalyst pellets can be optionally milled and or sieved to
obtain the desired particle size distribution.
[0233] In some embodiments, the catalyst materials, alone or with
binders and/or diluents, can be configured into larger aggregate
forms, such as pellets, extrudates, or other aggregations of
catalyst particles. For ease of duscussion, such larger forms are
generally referred to herein as "pellets". Such pellets may
optionally include a binder and/or support material; however, the
present inventors have surprisingly found that the disclosed
nanowires are particularly suited to used in the form of a pellet
without a binder and/or support material. Accordingly, one
embodiment of the disclosure provides a catalytic material in the
absence of a binder. In this regard, the morphology of the
disclosed nanowires (either bent or straight, etc.) is believed to
contribute to the nanowires' ability to be pressed into pellets
without the need for a binder. Catalytic materials without binders
are simpler, less complex and cheaper than corresponding materials
with binders and thus offer certain advantages.
[0234] In some instances, catalytic materials may be prepared using
a "sacrificial binder" or support. Because of their special
properties, the nanowires allow for preparation of catalytic
material forms (e.g. pellets) without the use of a binder. A
"sacrificial" binder can be used in order to create unique
microporosity in pellets or extrudates. After removing the
sacrificial binder, the structural integrity of the catalyst is
ensured by the special binding properties of the nanowires and the
resulting catalytic material has unique microporosity as a result
of removing the binder. For example, in some embodiments a
catalytic nanowire may be prepared with a binder and then the
binder removed by any number of techniques (e.g., combustion,
calcinations, acid erosion, etc.). This method allows for design
and preparation of catalytic materials having unique microporosity
(i.e., the microporosity is a function of size, etc. of the
sacrificial binder). The ability to prepare different forms (e.g.,
pellets) of the nanowires without the use of binder is not only
useful for preparation of catalytic materials from the nanowires,
but also allows the nanowires to be used as support materials (or
both catalytic and support material). Sacrificial binders and
techniques useful in this regard include sacrificial cellulosic
fibers or other organic polymers that can be easily removed by
calcination, non-sacrificial binders and techniques useful in this
regard include, colloidal oxide binders such as Ludox Silica or
Nyacol colloidal zirconia that can also be added to strengthen the
formed aggregate when needed. Sacrificial binders are added to
increase macro-porosity (pores larger than 20 nm diameter) of the
catalytic materials. Accordingly, in some embodiments the catalytic
materials comprise pores greater than 20 nm in diameter, greater
than 50 nm in diameter, greater than 75 nm in diameter, greater
than 100 nm in diameter or greater than 150 nm in diameter.
[0235] Catalytic materials also include any of the disclosed
nanowires disposed on or adhered to a solid support. For example,
the nanowires may be adhered to the surface of a monolith support.
As with the binder-less materials discussed above, in these
embodiments the nanowires may be adhered to the surface of the
monolith in the absence of a binder due to their unique morphology
and packing properties. Monoliths include honeycomb-type
structures, foams and other catalytic support structures derivable
by one skilled in the art. In one embodiment, the support is a
honeycomb matrix formed from silicon carbide, and the support
further comprises catalytic nanowires disposed on the surface.
[0236] As the OCM reaction is very exothermic, it can be desirable
to reduce the rate of conversion per unit volume of reactor in
order to avoid run away temperature rise in the catalyst bed that
can result in hot spots affecting performance and catalyst life.
One way to reduce the OCM reaction rate per unit volume of reactor
is to spread the active catalyst onto an inert support with
interconnected large pores as in ceramic or metallic foams
(including metal alloys having reduced reactivity with hydrocarbons
under OCM reaction conditions) or having arrays of channel as in
honeycomb structured ceramic or metal assembly.
[0237] In one embodiment, a catalytic material comprising a
catalytic nanowire as disclosed herein supported on a structured
support is provided. Examples of such structure supports include,
but are not limited to, metal foams, Silicon Carbide or Alumina
foams, corrugated metal foil arranged to form channel arrays,
extruded ceramic honeycomb, for example Cordierite (available from
Corning or NGK ceramics, USA), Silicon Carbide or Alumina.
[0238] Active catalyst loading on the structured support ranges
from 1 to 500 mg per ml of support component, for example from 5 to
100 mg per ml of structure support. Cell densities on honeycomb
structured support materials may range from 100 to 900 CPSI (cell
per square inch), for example 200 to 600 CPSI. Foam densities may
range from 10 to 100 PPI (pore per inch), for example 20 to 60
PPI.
[0239] In other embodiments, the exotherm of the OCM reaction may
be at least partially controlled by blending the active catalytic
material with catalytically inert material, and pressing or
extruding the mixture into shaped pellets or extrudates. In some
embodiments, these mixed particles may then be loaded into a
pack-bed reactor. The Extrudates or pellets comprise between 30% to
70% pore volume with 5% to 50% active catalyst weight fraction.
Useful inert materials in this regard include, but are not limited
to MgO, CaO, Al.sub.2O.sub.3, SiC and cordierite.
[0240] In addition to reducing the potential for hot spots within
the catalytic reactor, another advantage of using a structured
ceramic with large pore volume as a catalytic support is reduced
flow resistance at the same gas hourly space velocity versus a
pack-bed containing the same amount of catalyst.
[0241] Yet another advantage of using such supports is that the
structured support can be used to provide features difficult to
obtain in a pack-bed reactor. For example the support structure can
improve mixing or enabling patterning of the active catalyst
depositions through the reactor volume. Such patterning can consist
of depositing multiple layers of catalytic materials on the support
in addition to the OCM active component in order to affect
transport to the catalyst or combining catalytic functions as
adding O2-ODH activity, CO2-OCM activity or CO2-ODH activity to the
system in addition to O2-OCM active material. Another patterning
strategy can be to create bypass within the structure catalyst
essentially free of active catalyst to limit the overall conversion
within a given supported catalyst volume.
[0242] Yet another advantage is reduced heat capacity of the bed of
the structured catalyst over a pack bed a similar active catalyst
loading therefore reducing startup time.
[0243] Nanowire shaped catalysts are particularly well suited for
incorporation into pellets or extrudates or deposition onto
structured supports. Nanowire aggregates forming a mesh type
structure can have good adhesion onto rough surfaces.
[0244] The mesh like structure can also provide improved cohesion
in composite ceramic improving the mechanical properties of pellets
or extrudates containing the nanowire shaped catalyst
particles.
[0245] Alternatively, such nanowire on support or in pellet form
approaches can be used for other reactions besides OCM, such as
ODH, dry methane reforming, FT, and all other catalytic
reactions.
[0246] In yet another embodiment, the catalysts are packed in bands
forming a layered reactor bed. Each layer is composed by either a
catalyst of a particular type, morphology or size or a particular
blend of catalysts. In one embodiment, the catalysts blend may have
better sintering properties, i.e. lower tendency to sinter, then a
material in its pure form. Better sintering resistance is expected
to increase the catalyst's lifetime and improve the mechanical
properties of the reactor bed.
[0247] In yet other embodiments, the disclosure provides a
catalytic material comprising one or more different catalysts. The
catalysts may be a nanowire as disclosed herein and a different
catalyst for example a bulk catalysts. Mixtures of two or more
nanowire catalysts are also contemplated. The catalytic material
may comprise a catalyst, for example a nanowire catalyst, having
good OCM activity and a catalyst having good activity in the ODH
reaction. Either one or both of these catalysts may be nanowires as
disclosed herein.
[0248] On skilled in the art will recognize that various
combinations or alternatives of the above methods are possible, and
such variations are also included within the scope of the present
disclosure.
[0249] 5. Dopants
[0250] In further embodiments, the disclosure provides nanowires
comprising a dopant (i.e., doped nanowires). As noted above,
dopants or doping agents are impurities added to or incorporated
within a catalyst to optimize catalytic performance (e.g., increase
or decrease catalytic activity). As compared to the undoped
catalyst, a doped catalyst may increase or decrease the
selectivity, conversion, and/or yield of a catalytic reaction. In
one embodiment, nanowire dopants comprise one or more metal
elements, semi-metal elements, non-metal elements or combinations
thereof. Although oxygen is included in the group of nonmetal
elements, in certain embodiments oxygen is not considered a dopant.
For example, certain embodiments are directed to nanowires
comprising two, three or even four or more dopants, and the dopants
are non-oxygen dopants. Thus in these embodiments, a metal oxide
nanowire is not considered to be a metal nanowire doped with
oxygen. Analagously, in the case of mixed oxides (i.e.,
M1.sub.xM2.sub.yO.sub.z), both the metal elements and oxygen are
considered a part of the base catalyst (nanowire) and are not
included in the total number of dopants.
[0251] The dopant may be present in any form and may be derived
from any suitable source of the element (e.g., chlorides, bromides,
iodides, nitrates, oxynitrates, oxyhalides, acetates, formates,
hydroxides, carbonates, phosphates, sulfates, alkoxides, and the
like.). In some embodiments, the nanowire dopant is in elemental
form. In other embodiments, the nanowire dopant is in reduced or
oxidized form. In other embodiments, the nanowire dopant comprises
an oxide, hydroxide, carbonate, nitrate, acetate, sulfate, formate,
oxynitrate, halide, oxyhalide or hydroxyhalide of a metal element,
semi-metal element or non-metal element or combinations
thereof.
[0252] In one embodiment, the nanowires comprise one or more metal
elements selected from Groups 1-7, lanthanides, actinides or
combinations thereof in the form of an oxide and further comprise
one or more dopants, wherein the one or more dopants comprise metal
elements, semi-metal elements, non-metal elements or combinations
thereof. In another embodiment, the nanowires comprise one or more
metal elements selected from group 1 in the form of an oxide and
further comprise one or more dopants, wherein the one or more
dopants comprise metal elements, semi-metal elements, non-metal
elements or combinations thereof. In another embodiment, the
nanowires comprise one or more metal elements selected from group 2
in the form of an oxide and further comprise one or more dopants,
wherein the one or more dopants comprise metal elements, semi-metal
elements, non-metal elements or combinations thereof. In another
embodiment, the nanowires comprise one or more metal elements
selected from group 3 in the form of an oxide and further comprise
one or more dopants, wherein the one or more dopants comprise metal
elements, semi-metal elements, non-metal elements or combinations
thereof. In another embodiment, the nanowires comprise one or more
metal elements selected from group 4 in the form of an oxide and
further comprise one or more dopants, wherein the one or more
dopants comprise metal elements, semi-metal elements, non-metal
elements or combinations thereof. In another embodiment, the
nanowires comprise one or more metal elements selected from group 5
in the form of an oxide and further comprise one or more dopants,
wherein the one or more dopants comprise metal elements, semi-metal
elements, non-metal elements or combinations thereof. In another
embodiment, the nanowires comprise one or more metal elements
selected from group 6 in the form of an oxide and further comprise
one or more dopants, wherein the one or more dopants comprise metal
elements, semi-metal elements, non-metal elements or combinations
thereof. In another embodiment, the nanowires comprise one or more
metal elements selected from group 7 in the form of an oxide and
further comprise one or more dopants, wherein the one or more
dopants comprise metal elements, semi-metal elements, non-metal
elements or combinations thereof. In another embodiment, the
nanowires comprise one or more metal elements selected from
lanthanides in the form of an oxide and further comprise one or
more dopants, wherein the one or more dopants comprise metal
elements, semi-metal elements, non-metal elements or combinations
thereof. In another embodiment, the nanowires comprise one or more
metal elements selected from actinides in the form of an oxide and
further comprise one or more dopants, wherein the one or more
dopants comprise metal elements, semi-metal elements, non-metal
elements or combinations thereof.
[0253] For example, in one embodiment, the nanowire dopant
comprises Li, Li.sub.2CO.sub.3, LiOH, Li.sub.2O, LiCl, LiNO.sub.3,
Na, Na.sub.2CO.sub.3, NaOH, Na.sub.2O, NaCl, NaNO.sub.3, K,
K.sub.2CO.sub.3, KOH, K.sub.2O, KCl, KNO.sub.3, Rb,
Rb.sub.2CO.sub.3, RbOH, Rb.sub.2O, RbCl, RbNO.sub.3, Cs,
Cs.sub.2CO.sub.3, CsOH, Cs.sub.2O, CsCl, CsNO.sub.3, Mg,
MgCO.sub.3, Mg(OH).sub.2, MgO, MgCl.sub.2, Mg(NO.sub.3).sub.2, Ca,
CaO, CaCO.sub.3, Ca(OH).sub.2, CaCl.sub.2, Ca(NO.sub.3).sub.2, Sr,
SrO, SrCO.sub.3, Sr(OH).sub.2, SrCl.sub.2, Sr(NO.sub.3).sub.2, Ba,
BaO, BaCO.sub.3, Ba(OH).sub.2, BaCl.sub.2, Ba(NO.sub.3).sub.2, La,
La.sub.2O.sub.3, La.sub.2(CO.sub.3).sub.3, La(OH).sub.3,
LaCl.sub.3, La(NO.sub.3).sub.2, Nd, Nd.sub.2O.sub.3,
Nd.sub.2(CO.sub.3).sub.3, Nd(OH).sub.3, NdCl.sub.3,
Nd(NO.sub.3).sub.2, Sm, Sm.sub.2O.sub.3, Sm.sub.2(CO.sub.3).sub.3,
Sm(OH).sub.3, SmCl.sub.3, Sm(NO.sub.3).sub.2, Eu, Eu.sub.2O.sub.3,
Eu.sub.2(CO.sub.3).sub.3, Eu(OH).sub.3, EuCl.sub.3,
Eu(NO.sub.3).sub.2, Gd, Gd.sub.2O.sub.3, Gd.sub.2(CO.sub.3).sub.3,
Gd(OH).sub.3, GdCl.sub.3, Gd(NO.sub.3).sub.2, Ce, Ce(OH).sub.4,
CeO.sub.2, Ce.sub.2O.sub.3, Ce(CO.sub.3).sub.2, CeCl.sub.4,
Ce(NO.sub.3).sub.2, Th, ThO.sub.2, ThCl.sub.4, Th(OH).sub.4, Zr,
ZrO.sub.2, ZrCl.sub.4, Zr(OH).sub.4, ZrOCl.sub.2, Zr(CO.sub.3)2,
ZrOCO.sub.3, ZrO(NO.sub.3).sub.2, P, phosphorous oxides,
phosphorous chlorides, phosphorous carbonates, Ni, nickel oxides,
nickel chlorides, nickel carbonates, nickel hydroxides, Nb, niobium
oxides, niobium chlorides, niobium carbonates, niobium hydroxides,
Au, gold oxides, gold chlorides, gold carbonates, gold hydroxides,
Mo, molybdenum oxides, molybdenum chlorides, molybdenum carbonates,
molybdenum hydroxides, tungsten chlorides, tungsten carbonates,
tungsten hydroxides, Cr, chromium oxides, chromium chlorides,
chromium hydroxides, Mn, manganese oxides, manganese chlorides,
manganese hydroxides, Zn, ZnO, ZnCl.sub.2, Zn(OH).sub.2, B,
borates, BCl.sub.3, N, nitrogen oxides, nitrates, La, Ce, Pr, Nd,
Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Y, Sc, Al, Cu, Cs,
Ga, Hf, Fe, Ru, Rh, Be, Co, Sb, V, Ag, Te, Pd, Tb, Ir, Rb or
combinations thereof. In other embodiments, the nanowire dopant
comprises Li, Na, K, Rb, Cs, Mg, Ca, Sr, Eu, In, Nd, Sm, Ce, Gd,
Tb, Er, Tm, Yb, Y, Sc or combinations thereof.
[0254] In other embodiments, the nanowire dopant comprises Li,
Li.sub.2O, Na, Na.sub.2O, K, K.sub.2O, Mg, MgO, Ca, CaO, Sr, SrO,
Ba, BaO, La, La.sub.2O.sub.3, Ce, CeO.sub.2, Ce.sub.2O.sub.3, Th,
ThO.sub.2, Zr, ZrO.sub.2, P, phosphorous oxides, Ni, nickel oxides,
Nb, niobium oxides, Au, gold oxides, Mo, molybdenum oxides, Cr,
chromium oxides, Mn, manganese oxides, Zn, ZnO, B, borates, N,
nitrogen oxides or combinations thereof. In other embodiments, the
nanowire dopant comprises Li, Na, K, Mg, Ca, Sr, Ba, La, Ce, Th,
Zr, P, Ni, Nb, Au, Mo, Cr, Mn, Zn, B, N or combinations thereof. In
other embodiments, the nanowire dopant comprises Li.sub.2O,
Na.sub.2O, K.sub.2O, MgO, CaO, SrO, BaO, La.sub.2O.sub.3,
CeO.sub.2, Ce.sub.2O.sub.3, ThO.sub.2, ZrO.sub.2, phosphorous
oxides, nickel oxides, niobium oxides, gold oxides, molybdenum
oxides, chromium oxides, manganese oxides, ZnO, borates, nitrogen
oxides or combinations thereof. In further embodiments, the dopant
comprises Sr or Li. In other specific embodiments, the nanowire
dopant comprises La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu, In, Y, Sc or combinations thereof. In other specific
embodiments, the nanowire dopant comprises Li, Na, K, Mg, Ca, Ba,
Sr, Eu, Sm, Co or Mn.
[0255] In certain embodiments, the dopant comprises an element from
group 1. In some embodiments, the dopant comprises lithium. In some
embodiments, the dopant comprises sodium. In some embodiments, the
dopant comprises potassium. In some embodiments, the dopant
comprises rubidium. In some embodiments, the dopant comprises
caesium.
[0256] In some embodiments the nanowires comprise a lanthanide
element and are doped with a dopant from group 1, group 2, or
combinations thereof. For example, in some embodiments, the
nanowires comprise a lanthanide element and are doped with lithium.
In other embodiments, the nanowires comprise a lanthanide element
and are doped with sodium. In other embodiments, the nanowires
comprise a lanthanide element and are doped with potassium. In
other embodiments, the nanowires comprise a lanthanide element and
are doped with rubidium. In other embodiments, the nanowires
comprise a lanthanide element and are doped with caesium. In other
embodiments, the nanowires comprise a lanthanide element and are
doped with beryllium. In other embodiments, the nanowires comprise
a lanthanide element and are doped with magnesium. In other
embodiments, the nanowires comprise a lanthanide element and are
doped with calcium. In other embodiments, the nanowires comprise a
lanthanide element and are doped with strontium. In other
embodiments, the nanowires comprise a lanthanide element and are
doped with barium.
[0257] In some embodiments the nanowires comprise a transition
metal tungstate (e.g., Mn/W and the like) and are doped with a
dopant from group 1, group 2, or combinations thereof. For example,
in some embodiments, the nanowires comprise a transition metal
tungstate and are doped with lithium. In other embodiments, the
nanowires comprise a transition metal tungstate and are doped with
sodium. In other embodiments, the nanowires comprise a transition
metal tungstate and are doped with potassium. In other embodiments,
the nanowires comprise a transition metal tungstate and are doped
with rubidium. In other embodiments, the nanowires comprise a
transition metal tungstate and are doped with caesium. In other
embodiments, the nanowires comprise a transition metal tungstate
and are doped with beryllium. In other embodiments, the nanowires
comprise a transition metal tungstate and are doped with magnesium.
In other embodiments, the nanowires comprise a transition metal
tungstate and are doped with calcium. In other embodiments, the
nanowires comprise a transition metal tungstate and are doped with
strontium. In other embodiments, the nanowires comprises a
transition metal tungstate and are doped with barium.
[0258] In some embodiments the nanowires comprise Mn/Mg/O and are
doped with a dopant from group 1, group 2, group 7, group 8, group
9 or group 10 or combinations thereof. For example, in some
embodiments, the nanowires comprise Mn/Mg/O and are doped with
lithium. In other embodiments, the nanowires comprise Mn/Mg/O and
are doped with sodium. In other embodiments, the nanowires comprise
Mn/Mg/O and are doped with potassium. In other embodiments, the
nanowires comprise Mn/Mg/O and are doped with rubidium. In other
embodiments, the nanowires comprise Mn/Mg/O and are doped with
caesium. In other embodiments, the nanowires comprise Mn/Mg/O and
are doped with beryllium. In other embodiments, the nanowires
comprise Mn/Mg/O and are doped with magnesium. In other
embodiments, the nanowires comprise Mn/Mg/O and are doped with
calcium. In other embodiments, the nanowires comprise Mn/Mg/O and
are doped with strontium. In other embodiments, the nanowires
comprise Mn/Mg/O and are doped with barium.
[0259] In yet some other embodiments, the nanowires comprise
Mn/Mg/O and are doped with manganese. In other embodiments, the
nanowires comprise Mn/Mg/O and are doped with technetium. In other
embodiments, the nanowires comprise Mn/Mg/O and are doped with
rhenium. In other embodiments, the nanowires comprise Mn/Mg/O and
are doped with iron. In other embodiments, the nanowires comprise
Mn/Mg/O and are doped with ruthenium. In other embodiments, the
nanowires comprise Mn/Mg/O and are doped with osmium. In other
embodiments, the nanowires comprise Mn/Mg/O and are doped with
cobalt. In other embodiments, the nanowires comprise Mn/Mg/O and
are doped with rhodium. In other embodiments, the nanowires
comprise Mn/Mg/O and are doped with iridium. In other embodiments,
the nanowires comprise Mn/Mg/O and are doped with nickel. In other
embodiments, the nanowires comprise Mn/Mg/O and are doped with
palladium. In other embodiments, the nanowires comprise Mn/Mg/O and
are doped with platinum.
[0260] As noted above, the present inventors have determined that
certain nanowire catalysts comprising rare earth elements(e.g.,
rare earth oxides) are useful as catalysts in a number of
reactions, for example the OCM reaction. In certain embodiments the
rare earth element is La, Nd, Eu, Sm, Yb, Gd or Y. In some
embodiments, the rare earth element is La. In other embodiments,
the rare earth element is Nd. In other embodiments, the rare earth
element is Eu. In other embodiments, the rare earth element is Sm.
In other embodiments, the rare earth element is Yb. In other
embodiments, the rare earth element is Gd. In other embodiments,
the rare earth element is Y.
[0261] In certain embodiments of the nanowire catalysts comprising
rare earth elements, the catalyst may further comprise a dopant
selected from alkaline earth (Group 2) elements. For example, in
some embodiments the dopant is selected from Be, Mg, Ca, Sr and Ba.
In other embodiments, the dopant is Be. In other embodiments, the
dopant is Ca. In other embodiments, the dopant is Sr. In other
embodiments, the dopant is Ba.
[0262] In some embodiments, these rare earth compositions comprise
La.sub.2O.sub.3, Nd.sub.2O.sub.3, Yb.sub.2O.sub.3, Eu.sub.2O.sub.3,
Sm.sub.2O.sub.3, Y.sub.2O.sub.3, Ce.sub.2O.sub.3, Pr.sub.2O.sub.3,
Ln1.sub.4-xLn2.sub.xO.sub.6, La.sub.4-xLn1.sub.xO.sub.6,
La.sub.4-xNd.sub.xO.sub.6, La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6,
La.sub.1.5Nd.sub.2.5O.sub.6, La.sub.2.5Nd.sub.1.5O.sub.6,
La.sub.3.2Nd.sub.0.8O.sub.6, La.sub.3.5Nd.sub.0.5O.sub.6,
La.sub.3.8Nd.sub.0.2O.sub.6, Y--La, Zr--La, Pr--La or Ce--La or
combinations thereof, wherein Ln1 and Ln2 are each independently a
lanthanide element, wherein Ln1 and Ln2 are not the same and x is a
number ranging from greater than 0 to less than 4.
[0263] Further, Applicants have discovered that certain doping
combinations, when combined with the above rare earth compositions,
serve to enhance the catalytic activity of the nanowires in certain
catalytic reactions, for example OCM. The dopants may be present in
various levels (e.g., w/w), and the nanowires may be prepared by
any number of methods. Various aspects of the above nanowires are
provided in the following paragraphs and in Tables 9-12.
[0264] In certain embodiments, the above rare earth compositions
comprise a strontium dopant and at least one more additional dopant
selected from group 1, 4-6, 13 and lanthanides. For example, in
some embodiments the additional dopant is Hf, K, Zr, Ce, Tb, Pr, W,
Rb, Ta, B or combinations thereof. In other embodiments, the dopant
comprises Sr/Hf, Sr/Hf/K, Sr/Zr, Sr/Zr/K, Sr/Ce, Sr/Ce/K, Sr/Tb,
Sr/Tb/K, Sr/Pr, Sr/Pr/K, Sr/W, Sr/Hf/Rb, Sr/Ta or Sr/B. In some
other embodiments, the foregoing rare earth nanowires comprise
La.sub.2O.sub.3 or La.sub.3NdO.sub.6.
[0265] In other embodiments, the nanowire catalysts comprise a rare
earth oxide and dopants selected from at least one of the following
combinations Eu/Na, Sr/Na, Mg/Na, Sr/W, K/La, K/Na, Li/Cs, Li/Na,
Zn/K, Li/K, Rb/Hf, Ca/Cs, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W,
Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi,
Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W,
Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re,
Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce, Li/Sr, Cs/Zn, Dy/K, La/Mg, In/Sr,
Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy, Mg/K, Zr/K, Li/Cs, Sm/Cs, In/K,
Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce, Ba/Ta, Cu/Sn, Ag/Au, Al/Bi,
Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho,
Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb and Sr/Hf.
[0266] In still other embodiments, the nanowire catalysts comprise
a rare earth oxide and dopants selected from at least one of the
following combinations La/Nd, La/Sm, La/Ce, La/Sr, Eu/Na, Eu/Gd,
Ca/Na, Eu/Sm, Eu/Sr, Mg/Sr, Ce/Mg, Gd/Sm, Sr/W, Sr/Ta, Au/Re,
Au/Pb, Bi/Hf, Sr/Sn or Mg/N, Ca/S, Rb/S, Sr/Nd, Eu/Y, Mg/Nd, Sr/Na,
Nd/Mg, La/Mg, Yb/S, Mg/Na, Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K,
Li/K, Rb/Hf, Ca/Cs, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W,
Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi,
Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W,
Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re,
Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce, Li/Sr, Cs/Zn, Dy/K, La/Mg, In/Sr,
Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy, Mg/K, Zr/K, Li/Cs, Sm/Cs, In/K,
Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce, Ba/Ta, Cu/Sn, Ag/Au, Al/Bi,
Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho,
Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb and Sr/Hf.
[0267] In other embodiments of the foregoing rare earth oxide
nanowire catalysts, the nanowire catalysts comprise a combination
of two doping elements. In some embodiments, the combination of two
doping elements is La/Nd. In other embodiments, the combination of
two doping elements is La/Sm. In other embodiments, the combination
of two doping elements is La/Ce. In other embodiments, the
combination of two doping elements is La/Sr. In other embodiments,
the combination of two doping elements is Eu/Na. In other
embodiments, the combination of two doping elements is Eu/Gd. In
other embodiments, the combination of two doping elements is Ca/Na.
In other embodiments, the combination of two doping elements is
Eu/Sm. In other embodiments, the combination of two doping elements
is Eu/Sr. In other embodiments, the combination of two doping
elements is Mg/Sr. In other embodiments, the combination of two
doping elements is Ce/Mg. In other embodiments, the combination of
two doping elements is Gd/Sm. In other embodiments, the combination
of two doping elements is Sr/W. In other embodiments, the
combination of two doping elements is Sr/Ta. In other embodiments,
the combination of two doping elements is Au/Re. In other
embodiments, the combination of two doping elements is Au/Pb. In
other embodiments, the combination of two doping elements is Bi/Hf.
In other embodiments, the combination of two doping elements is
Sr/Sn. In other embodiments, the combination of two doping elements
is Mg/N. In other embodiments, the combination of two doping
elements is Ca/S. In other embodiments, the combination of two
doping elements is Rb/S. In other embodiments, the combination of
two doping elements is Sr/Nd. In other embodiments, the combination
of two doping elements is Eu/Y. In other embodiments, the
combination of two doping elements is Mg/Nd. In other embodiments,
the combination of two doping elements is Sr/Na. In other
embodiments, the combination of two doping elements is Nd/Mg. In
other embodiments, the combination of two doping elements is La/Mg.
In other embodiments, the combination of two doping elements is
Yb/S. In other embodiments, the combination of two doping elements
is Mg/Na. In other embodiments, the combination of two doping
elements is Sr/W. In other embodiments, the combination of two
doping elements is K/La. In other embodiments, the combination of
two doping elements is K/Na. In other embodiments, the combination
of two doping elements is Li/Cs. In other embodiments, the
combination of two doping elements is Li/Na. In other embodiments,
the combination of two doping elements is Zn/K. In other
embodiments, the combination of two doping elements is Li/K. In
other embodiments, the combination of two doping elements is Rb/Hf.
In other embodiments, the combination of two doping elements is
Ca/Cs. In other embodiments, the combination of two doping elements
is Hf/Bi. In other embodiments, the combination of two doping
elements is Sr/Sn. In other embodiments, the combination of two
doping elements is Sr/W. In other embodiments, the combination of
two doping elements is Sr/Nb. In other embodiments, the combination
of two doping elements is Zr/W. In other embodiments, the
combination of two doping elements is Y/W. In other embodiments,
the combination of two doping elements is Na/W. In other
embodiments, the combination of two doping elements is Bi/W. In
other embodiments, the combination of two doping elements is Bi/Cs.
In other embodiments, the combination of two doping elements is
Bi/Ca. In other embodiments, the combination of two doping elements
is Bi/Sn. In other embodiments, the combination of two doping
elements is Bi/Sb. In other embodiments, the combination of two
doping elements is Ge/Hf. In other embodiments, the combination of
two doping elements is Hf/Sm. In other embodiments, the combination
of two doping elements is Sb/Ag. In other embodiments, the
combination of two doping elements is Sb/Bi. In other embodiments,
the combination of two doping elements is Sb/Au. In other
embodiments, the combination of two doping elements is Sb/Sm. In
other embodiments, the combination of two doping elements is Sb/Sr.
In other embodiments, the combination of two doping elements is
Sb/W. In other embodiments, the combination of two doping elements
is Sb/Hf. In other embodiments, the combination of two doping
elements is Sb/Yb. In other embodiments, the combination of two
doping elements is Sb/Sn. In other embodiments, the combination of
two doping elements is Yb/Au. In other embodiments, the combination
of two doping elements is Yb/Ta. In other embodiments, the
combination of two doping elements is Yb/W. In other embodiments,
the combination of two doping elements is Yb/Sr. In other
embodiments, the combination of two doping elements is Yb/Pb. In
other embodiments, the combination of two doping elements is Yb/W.
In other embodiments, the combination of two doping elements is
Yb/Ag. In other embodiments, the combination of two doping elements
is Au/Sr. In other embodiments, the combination of two doping
elements is W/Ge. In other embodiments, the combination of two
doping elements is Ta/Hf. In other embodiments, the combination of
two doping elements is W/Au. In other embodiments, the combination
of two doping elements is Ca/W. In other embodiments, the
combination of two doping elements is Au/Re. In other embodiments,
the combination of two doping elements is Sm/Li. In other
embodiments, the combination of two doping elements is La/K. In
other embodiments, the combination of two doping elements is Zn/Cs.
In other embodiments, the combination of two doping elements is
Zr/Cs. In other embodiments, the combination of two doping elements
is Ca/Ce. In other embodiments, the combination of two doping
elements is Li/Sr. In other embodiments, the combination of two
doping elements is Cs/Zn. In other embodiments, the combination of
two doping elements is Dy/K. In other embodiments, the combination
of two doping elements is La/Mg. In other embodiments, the
combination of two doping elements is In/Sr. In other embodiments,
the combination of two doping elements is Sr/Cs. In other
embodiments, the combination of two doping elements is Ga/Cs. In
other embodiments, the combination of two doping elements is Lu/Fe.
In other embodiments, the combination of two doping elements is
Sr/Tm. In other embodiments, the combination of two doping elements
is La/Dy. In other embodiments, the combination of two doping
elements is Mg/K. In other embodiments, the combination of two
doping elements is Zr/K. In other embodiments, the combination of
two doping elements is Li/Cs. In other embodiments, the combination
of two doping elements is Sm/Cs. In other embodiments, the
combination of two doping elements is In/K. In other embodiments,
the combination of two doping elements is Lu/Tl. In other
embodiments, the combination of two doping elements is Pr/Zn. In
other embodiments, the combination of two doping elements is Lu/Nb.
In other embodiments, the combination of two doping elements is
Na/Pt. In other embodiments, the combination of two doping elements
is Na/Ce. In other embodiments, the combination of two doping
elements is Ba/Ta. In other embodiments, the combination of two
doping elements is Cu/Sn. In other embodiments, the combination of
two doping elements is Ag/Au. In other embodiments, the combination
of two doping elements is Al/Bi. In other embodiments, the
combination of two doping elements is Al/Mo. In other embodiments,
the combination of two doping elements is Al/Nb. In other
embodiments, the combination of two doping elements is Au/Pt. In
other embodiments, the combination of two doping elements is Ga/Bi.
In other embodiments, the combination of two doping elements is
Mg/W. In other embodiments, the combination of two doping elements
is Pb/Au. In other embodiments, the combination of two doping
elements is Sn/Mg. In other embodiments, the combination of two
doping elements is Zn/Bi. In other embodiments, the combination of
two doping elements is Gd/Ho. In other embodiments, the combination
of two doping elements is Zr/Bi. In other embodiments, the
combination of two doping elements is Ho/Sr. In other embodiments,
the combination of two doping elements is Ca/Sr. In other
embodiments, the combination of two doping elements is Sr/Pb. In
other embodiments, the combination of two doping elements is
Sr/Hf.
[0268] In still other embodiments, the nanowire catalysts comprise
a rare earth oxide and dopants selected from at least one of the
following combinations Mg/La/K, Na/Dy/K, Na/La/Dy, Na/La/Eu,
Na/La/K, K/La/S, Li/Cs/La, Li/Sr/Cs, Li/Ga/Cs, Li/Na/Sr, Li/Sm/Cs,
Cs/K/La, Sr/Cs/La, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Rb/Sr/Lu, Na/Eu/Hf,
Dy/Rb/Gd, Na/Pt/Bi, Ca/Mg/Na, Na/K/Mg, Na/Li/Cs, La/Dy/K, Sm/Li/Sr,
Li/Rb/Ga, Li/Cs/Tm, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La,
Cs/La/Na, La/S/Sr, Rb/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, La/Dy/Gd, Gd/Li/K,
Rb/K/Lu, Na/Ce/Co, Ba/Rh/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb, Hf/Zr/Ta,
Na/Ca/Lu, Gd/Ho/Sr, Ca/Sr/W, Na/Zr/Eu/Tm, Sr/W/Li, Ca/Sr/W or
Mg/Nd/Fe.
[0269] In more embodiments, the nanowire catalysts comprise a rare
earth oxide and dopants selected from at least one of the following
combinations Nd/Sr/CaO, La/Nd/Sr, La/Bi/Sr, Mg/Nd/Fe, Mg/La/K,
Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/K, K/La/S, Li/Cs/La, Li/Sr/Cs,
Li/Ga/Cs, Li/Na/Sr, Li/Sm/Cs, Cs/K/La, Sr/Cs/La, Sr/Ho/Tm, La/Nd/S,
Li/Rb/Ca, Rb/Sr/Lu, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Ca/Mg/Na,
Na/K/Mg, Na/Li/Cs, La/Dy/K, Sm/Li/Sr, Li/Rb/Ga, Li/Cs/Tm, Li/K/La,
Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Cs/La/Na, La/S/Sr, Rb/Sr/La,
Na/Sr/Lu, Sr/Eu/Dy, La/Dy/Gd, Gd/Li/K, Rb/K/Lu, Na/Ce/Co, Ba/Rh/Ta,
Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb, Hf/Zr/Ta, Na/Ca/Lu, Gd/Ho/Sr, Ca/Sr/W,
Na/Zr/Eu/Tm, Sr/W/Li or Ca/Sr/W.
[0270] In other embodiments of the foregoing rare earth oxide
nanowire catalysts, the nanowire catalysts comprise a combination
of at least three doping elements. In some embodiments, the
combination of at least three different doping elements is
Nd/Sr/CaO. In other embodiments, the combination of at least three
different doping elements is La/Nd/Sr. In other embodiments, the
combination of at least three different doping elements is
La/Bi/Sr. In other embodiments, the combination of at least three
different doping elements is Mg/Nd/Fe. In other embodiments, the
combination of at least three different doping elements is Mg/La/K.
In other embodiments, the combination of at least three different
doping elements is Na/Dy/K. In other embodiments, the combination
of at least three different doping elements is Na/La/Dy. In other
embodiments, the combination of at least three different doping
elements is Na/La/Eu. In other embodiments, the combination of at
least three different doping elements is Na/La/K. In other
embodiments, the combination of at least three different doping
elements is K/La/S. In other embodiments, the combination of at
least three different doping elements is Li/Cs/La. In other
embodiments, the combination of at least three different doping
elements is Li/Sr/Cs. In other embodiments, the combination of at
least three different doping elements is Li/Ga/Cs. In other
embodiments, the combination of at least three different doping
elements is Li/Na/Sr. In other embodiments, the combination of at
least three different doping elements is Li/Sm/Cs. In other
embodiments, the combination of at least three different doping
elements is Cs/K/La. In other embodiments, the combination of at
least three different doping elements is Sr/Cs/La. In other
embodiments, the combination of at least three different doping
elements is Sr/Ho/Tm. In other embodiments, the combination of at
least three different doping elements is La/Nd/S. In other
embodiments, the combination of at least three different doping
elements is Li/Rb/Ca. In other embodiments, the combination of at
least three different doping elements is Rb/Sr/Lu. In other
embodiments, the combination of at least three different doping
elements is Na/Eu/Hf. In other embodiments, the combination of at
least three different doping elements is Dy/Rb/Gd. In other
embodiments, the combination of at least three different doping
elements is Na/Pt/Bi. In other embodiments, the combination of at
least three different doping elements is Ca/Mg/Na. In other
embodiments, the combination of at least three different doping
elements is Na/K/Mg. In other embodiments, the combination of at
least three different doping elements is Na/Li/Cs. In other
embodiments, the combination of at least three different doping
elements is La/Dy/K. In other embodiments, the combination of at
least three different doping elements is Sm/Li/Sr. In other
embodiments, the combination of at least three different doping
elements is Li/Rb/Ga. In other embodiments, the combination of at
least three different doping elements is Li/Cs/Tm. In other
embodiments, the combination of at least three different doping
elements is Li/K/La. In other embodiments, the combination of at
least three different doping elements is Ce/Zr/La. In other
embodiments, the combination of at least three different doping
elements is Ca/Al/La. In other embodiments, the combination of at
least three different doping elements is Sr/Zn/La. In other
embodiments, the combination of at least three different doping
elements is Cs/La/Na. In other embodiments, the combination of at
least three different doping elements is La/S/Sr. In other
embodiments, the combination of at least three different doping
elements is Rb/Sr/La. In other embodiments, the combination of at
least three different doping elements is Na/Sr/Lu. In other
embodiments, the combination of at least three different doping
elements is Sr/Eu/Dy. In other embodiments, the combination of at
least three different doping elements is La/Dy/Gd. In other
embodiments, the combination of at least three different doping
elements is Gd/Li/K. In other embodiments, the combination of at
least three different doping elements is Rb/K/Lu. In other
embodiments, the combination of at least three different doping
elements is Na/Ce/Co. In other embodiments, the combination of at
least three different doping elements is Ba/Rh/Ta. In other
embodiments, the combination of at least three different doping
elements is Na/Al/Bi. In other embodiments, the combination of at
least three different doping elements is Cs/Eu/S. In other
embodiments, the combination of at least three different doping
elements is Sm/Tm/Yb. In other embodiments, the combination of at
least three different doping elements is Hf/Zr/Ta. In other
embodiments, the combination of at least three different doping
elements is Na/Ca/Lu. In other embodiments, the combination of at
least three different doping elements is Gd/Ho/Sr. In other
embodiments, the combination of at least three different doping
elements is Ca/Sr/W. In other embodiments, the combination of at
least three different doping elements is Na/Zr/Eu/Tm. In other
embodiments, the combination of at least three different doping
elements is Sr/W/Li. In other embodiments, the combination of at
least three different doping elements is Ca/Sr/W.
[0271] As noted above, certain doping combinations have been found
useful in various catalytic reactions, such as OCM. Thus, in one
embodiment, the catalytic nanowire comprises a combination of at
least four different doping elements, wherein the doping elements
are selected from a metal element, a semi-metal element and a
non-metal element. For example in certain embodiments the catalytic
nanowire comprises a metal oxide, and in other embodiments the
catalytic nanowire comprises a lanthanide metal. Still other
embodiments provide a catalytic nanowire comprising
La.sub.2O.sub.3, Nd.sub.2O.sub.3, Yb.sub.2O.sub.3, Eu.sub.2O.sub.3,
Sm.sub.2O.sub.3, Y.sub.2O.sub.3, Ce.sub.2O.sub.3, Pr.sub.2O.sub.3
or combinations thereof. In still other embodiments, the doping
elements do not include at least one of Li, B, Na, Co or Ga, and in
other embodiments the nanowires do not comprise Mg and/or Mn.
[0272] In other embodiments, the catalytic nanowire comprises a
lanthanide oxide, for example a lanthanide mixed oxide, for example
in some embodiments the catalytic nanowire comprises
Ln1.sub.4-xLn2.sub.xO.sub.6, wherein Ln1 and Ln2 are each
independently a lanthanide element, wherein Ln1 and Ln2 are not the
same and x is a number ranging from greater than 0 to less than 4.
In other embodiments, the catalytic nanowire comprises
La.sub.4-xNd.sub.xO.sub.6, wherein x is a number ranging from
greater than 0 to less than 4, and in still other embodiments, the
catalytic nanowire comprises La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6,
La.sub.1.5Nd.sub.2.5O.sub.6, La.sub.2.5Nd.sub.1.5O.sub.6,
La.sub.3.2Nd.sub.0.8O.sub.6, La.sub.3.5Nd.sub.0.5O.sub.6,
La.sub.3.8Nd.sub.0.2O.sub.6 or combinations thereof. In certain
other embodiments the mixed oxide comprises Y--La, Zr--La, Pr--La,
Ce--La or combinations thereof.
[0273] In other embodiments, the doping elements are selected from
Eu, Na, Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn,
Ga, Rb, Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge,
Ag, Au, Pb, B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo. For
example, in some embodiments, the combination of at least four
different doping elements is: Na/Zr/Eu/Ca, Sr/Sm/Ho/Tm, Na/K/Mg/Tm,
Na/La/Eu/In, Na/La/Li/Cs, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs,
Li/Sr/Zn/K, Li/K/Sr/La, Li/Na/Rb/Ga, Li/Na/Sr/La, Ba/Sm/Yb/S,
Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs,
Sr/Tm/Li/Cs, Zr/Cs/K/La, Rb/Ca/In/Ni, Tm/Lu/Ta/P, Rb/Ca/Dy/P,
Mg/La/Yb/Zn, Na/Sr/Lu/Nb, Na/Nd/In/K, Rb/Ga/Tm/Cs, K/La/Zr/Ag,
Ho/Cs/Li/La, K/La/Zr/Ag, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Mg/Tl/P,
Sr/La/Dy/S, Na/Ga/Gd/Al, Sm/Tm/Yb/Fe, Rb/Gd/Li/K, Gd/Ho/Al/P,
Na/Zr/Eu/Tm Sr/Ho/Tm/Na or Rb/Ga/Tm/Cs or La/Bi/Ce/Nd/Sr.
[0274] In other embodiments, the combination of at least four
different doping elements is Sr/Sm/Ho/Tm. In other embodiments, the
combination of at least four different doping elements is
Na/K/Mg/Tm. In other embodiments, the combination of at least four
different doping elements is Na/La/Eu/In. In other embodiments, the
combination of at least four different doping elements is
Na/La/Li/Cs. In other embodiments, the combination of at least four
different doping elements is Li/Cs/La/Tm. In other embodiments, the
combination of at least four different doping elements is
Li/Cs/Sr/Tm. In other embodiments, the combination of at least four
different doping elements is Li/Sr/Zn/K. In other embodiments, the
combination of at least four different doping elements is Li/Ga/Cs.
In other embodiments, the combination of at least four different
doping elements is Li/K/Sr/La. In other embodiments, the
combination of at least four different doping elements is
Li/Na/Rb/Ga. In other embodiments, the combination of at least four
different doping elements is Li/Na/Sr/La. In other embodiments, the
combination of at least four different doping elements is
Ba/Sm/Yb/S. In other embodiments, the combination of at least four
different doping elements is Ba/Tm/K/La. In other embodiments, the
combination of at least four different doping elements is
Ba/Tm/Zn/K. In other embodiments, the combination of at least four
different doping elements is Cs/La/Tm/Na. In other embodiments, the
combination of at least four different doping elements is
Cs/Li/K/La. In other embodiments, the combination of at least four
different doping elements is Sm/Li/Sr/Cs. In other embodiments, the
combination of at least four different doping elements is
Sr/Tm/Li/Cs. In other embodiments, the combination of at least four
different doping elements is Zr/Cs/K/La. In other embodiments, the
combination of at least four different doping elements is
Rb/Ca/In/Ni. In other embodiments, the combination of at least four
different doping elements is Tm/Lu/Ta/P. In other embodiments, the
combination of at least four different doping elements is
Rb/Ca/Dy/P. In other embodiments, the combination of at least four
different doping elements is Mg/La/Yb/Zn. In other embodiments, the
combination of at least four different doping elements is
Na/Sr/Lu/Nb. In other embodiments, the combination of at least four
different doping elements is Na/Nd/In/K. In other embodiments, the
combination of at least four different doping elements is
K/La/Zr/Ag. In other embodiments, the combination of at least four
different doping elements is Ho/Cs/Li/La. In other embodiments, the
combination of at least four different doping elements is
K/La/Zr/Ag. In other embodiments, the combination of at least four
different doping elements is Na/Sr/Eu/Ca. In other embodiments, the
combination of at least four different doping elements is
K/Cs/Sr/La. In other embodiments, the combination of at least four
different doping elements is Na/Mg/Tl/P. In other embodiments, the
combination of at least four different doping elements is
Sr/La/Dy/S. In other embodiments, the combination of at least four
different doping elements is Na/Ga/Gd/Al. In other embodiments, the
combination of at least four different doping elements is
Sm/Tm/Yb/Fe. In other embodiments, the combination of at least four
different doping elements is Rb/Gd/Li/K. In other embodiments, the
combination of at least four different doping elements is
Gd/Ho/Al/P. In other embodiments, the combination of at least four
different doping elements is Na/Zr/Eu/T. In other embodiments, the
combination of at least four different doping elements is
Sr/Ho/Tm/Na. In other embodiments, the combination of at least four
different doping elements is Na/Zr/Eu/Ca. In other embodiments, the
combination of at least four different doping elements is
Rb/Ga/Tm/Cs. In other embodiments, the combination of at least four
different doping elements is La/Bi/Ce/Nd/Sr.
[0275] In other embodiments, the catalytic nanowire comprises at
least two different doping elements, wherein the doping elements
are selected from a metal element, a semi-metal element and a
non-metal element, and wherein at least one of the doping elements
is K, Sc, Ti, V, Nb, Ru, Os, Ir, Cd, In, Tl, S, Se, Po, Pr, Tb, Dy,
Ho, Er, Tm, Lu or an element selected from any of groups 6, 7, 10,
11, 14, 15 or 17. In some embodiments, at least one of the doping
elements is K, Ti, V, Nb, Ru, Os, Ir, Cd, In, Tl, S, Se, Po, Pr,
Tb, Dy, Ho, Er, Tm, Lu or an element selected from any of groups
10, 11, 14, 15 or 17. In certain other embodiments of the foregoing
catalytic nanowire, the catalytic nanowire comprises a metal oxide,
and in other embodiments the catalytic nanowire comprises a
lanthanide metal. In still other embodiments the catalytic nanowire
comprises La.sub.2O.sub.3, Nd.sub.2O.sub.3, Yb.sub.2O.sub.3,
Eu.sub.2O.sub.3, Sm.sub.2O.sub.3, Y.sub.2O.sub.3, Ce.sub.2O.sub.3,
Pr.sub.2O.sub.3 or combinations thereof.
[0276] In other embodiments of the foregoing catalytic nanowire,
the catalytic nanowire comprises a lanthanide oxide, for example a
lanthanide mixed oxide, for example in some embodiments the
catalytic nanowire comprises Ln1.sub.4-xLn2.sub.xO.sub.6, wherein
Ln1 and Ln2 are each independently a lanthanide element, wherein
Ln1 and Ln2 are not the same and x is a number ranging from greater
than 0 to less than 4. In other embodiments, the catalytic nanowire
comprises La.sub.4-xNd.sub.xO.sub.6, wherein x is a number ranging
from greater than 0 to less than 4, and in still other embodiments,
the catalytic nanowire comprises La.sub.3NdO.sub.6,
LaNd.sub.3O.sub.6, La.sub.1.5Nd.sub.2.5O.sub.6,
La.sub.2.5Nd.sub.1.5O.sub.6, La.sub.3.2Nd.sub.0.8O.sub.6,
La.sub.3.5Nd.sub.0.5O.sub.6, La.sub.3.8Nd.sub.0.2O.sub.6 or
combinations thereof. In certain other embodiments the mixed oxide
comprises Y--La, Zr--La, Pr--La, Ce--La or combinations
thereof.
[0277] In other embodiments of the nanowire comprising at least two
doping elements, the doping elements are selected from Eu, Na, Sr,
Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba,
Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb,
B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo.
[0278] In yet another aspect, the present disclosure provides a
catalytic nanowire comprising at least one of the following dopant
combinations: Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W,
Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Sr/Hf/K, Na/La/Eu,
Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs,
Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs,
Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr,
Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La,
Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K,
Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K,
Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb,
Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi,
Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca,
Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr,
Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W,
Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K,
Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,
Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs,
K/La/Zr/Ag, Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr,
Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La,
Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na,
La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,
K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,
Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al,
Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,
Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,
Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,
Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na,
Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.
[0279] In other embodiments of the foregoing catalytic nanowire,
the dopant is selected from Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb,
Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi,
Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho,
Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Na/Zr/Eu/Tm, Sr/Ho/Tm/Na,
Sr/Pb, Ca, Sr/W/Li, Ca/Sr/W, Sr/Hf, Eu/Na, Sr/Na, Na/Zr/Eu/Ca,
Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy,
Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na,
Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K,
Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga and Li/Na/Sr.
[0280] In still other embodiments of the foregoing catalytic
nanowire the dopant is selected from Li/Na/Sr/La, Li/Sm/Cs,
Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na,
Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La,
Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P,
Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd,
Na/Pt/Bi, Rb/Hf, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm, La/Dy, Sm/Li/Sr,
Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La,
Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Cs/La/Na, La/S/Sr,
K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La,
Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt, Gd/Li/K,
Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta,
Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,
Gd/Ho/Al/P and Na/Ca/Lu.
[0281] In still other embodiments of the foregoing catalytic
nanowire, the dopant is selected from Ta/Hf, W/Au, Ca/W, Au/Re,
Sm/Li, La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn,
La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs,
K/La/Zr/Ag, Lu/Fe, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga,
Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La,
Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Cs/La/Na, La/S/Sr, K/La/Zr/Ag,
Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu,
Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Li/Sr/Cs,
Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr,
Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/K/La,
Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K,
Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K,
Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb,
Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn,
Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb,
Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf,
Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr
and W/Ge.
[0282] For example in certain embodiments of the foregoing
catalytic nanowire, the catalytic nanowire comprises a metal oxide,
and in other embodiments the catalytic nanowire comprises a
lanthanide metal. In still other embodiments, the catalytic
nanowire comprises La.sub.2O.sub.3, Nd.sub.2O.sub.3,
Yb.sub.2O.sub.3, Eu.sub.2O.sub.3, Sm.sub.2O.sub.3, Y.sub.2O.sub.3,
Ce.sub.2O.sub.3, Pr.sub.2O.sub.3 or combinations thereof.
[0283] In other embodiments of the foregoing nanowire, the
catalytic nanowire comprises a lanthanide oxide, for example a
lanthanide mixed oxide, for example in some embodiments the
catalytic nanowire comprises Ln1.sub.4-xLn2.sub.xO.sub.6, wherein
Ln1 and Ln2 are each independently a lanthanide element, wherein
Ln1 and Ln2 are not the same and x is a number ranging from greater
than 0 to less than 4. In other embodiments, the catalytic nanowire
comprises La.sub.4-xNd.sub.xO.sub.6, wherein x is a number ranging
from greater than 0 to less than 4, and in still other embodiments,
the catalytic nanowire comprises La.sub.3NdO.sub.6,
LaNd.sub.3O.sub.6, La.sub.1.5Nd.sub.2.5O.sub.6,
La.sub.2.5Nd.sub.1.5O.sub.6, La.sub.3.2Nd.sub.0.8O.sub.6,
La.sub.3.5Nd.sub.0.5O.sub.6, La.sub.3.8Nd.sub.0.2O.sub.6 or
combinations thereof. In certain other embodiments the mixed oxide
comprises Y--La, Zr--La, Pr--La, Ce--La or combinations
thereof.
[0284] In still other embodiments, the disclosure provides a
catalytic nanowire comprising Ln1.sub.4-xLn2.sub.xO.sub.6 and a
dopant comprising a metal element, a semi-metal element, a
non-metal element or combinations thereof, wherein Ln1 and Ln2 are
each independently a lanthanide element, wherein Ln1 and Ln2 are
not the same and x is a number ranging from greater than 0 to less
than 4. For example, in certain embodiments the catalytic nanowire
comprises La.sub.4-xLn1.sub.xO.sub.6, wherein Ln1 is a lanthanide
element and x is a number ranging from greater than 0 to less than
4, and in other specific embodiments, the catalytic nanowire
comprises La.sub.4-xNd.sub.xO.sub.6, wherein x is a number ranging
from greater than 0 to less than 4.
[0285] Still further embodiments of the foregoing nanowire include
embodiments wherein the catalytic nanowire comprises comprises
La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6, La.sub.1.5Nd.sub.2.5O.sub.6,
La.sub.2.5Nd.sub.1.5O.sub.6, La.sub.3.2Nd.sub.0.8O.sub.6,
La.sub.35Nd.sub.0.5O.sub.6, La.sub.38Nd.sub.0.2O.sub.6 or
combinations thereof.
[0286] In other embodiments, the dopant is selected from: Eu, Na,
Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb,
Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au,
Pb, B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo. For example in
certain embodiments, the catalytic nanowire comprises at least one
of the following dopant combinations: Eu/Na, Sr/Na, Na/Zr/Eu/Ca,
Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy,
Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S,
K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs,
Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr,
Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K,
Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La,
Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S,
Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu,
Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf, Ca/Cs,
Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,
Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi,
Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W,
Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W,
Au/Re, Sm/Li, La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr,
Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs,
Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K,
Sr/Pr, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La,
Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Sr/Pr/K,
Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,
K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,
Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al,
Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,
Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,
Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,
Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na,
Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.
[0287] In other embodiments, the disclosure provides a nanowire
comprising a mixed oxide of Y--La, Zr--La, Pr--La, Ce--La or
combinations thereof and at least one dopant selected from a metal
element, a semi-metal element and a non-metal element. For example,
in some embodiments the at least one dopant is selected from Eu,
Na, Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga,
Rb, Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag,
Au, Pb, B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo, and in even
other embodiments, the catalytic nanowire comprises at least one of
the following dopant combinations: Eu/Na, Sr/Na, Na/Zr/Eu/Ca,
Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy,
Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S,
K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs,
Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr,
Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K,
Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La,
Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S,
Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu,
Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf, Ca/Cs,
Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,
Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi,
Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W,
Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W,
Au/Re, Sm/Li, La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr,
Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs,
Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K,
Sr/Pr, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La,
Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Sr/Pr/K,
Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,
K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,
Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al,
Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,
Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,
Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,
Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na,
Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.
[0288] In still other embodiments, the invention provides a
catalytic nanowire comprising a mixed oxide of a rare earth element
and a Group 13 element, wherein the catalytic nanowire further
comprises one or more Group 2 elements. In some embodiments, the
Group 13 element is B, Al, Ga or In. In other embodiments, the
Group 2 element is Ca or Sr. In still other embodiments, the rare
earth element is La, Y, Nd, Yb, Sm, Pr, Ce or Eu.
[0289] Examples of the foregoing catalytic nanowires include
catalytic nanowires comprising CaLnBO.sub.x, CaLnAlO.sub.x,
CaLnGaO.sub.x, CaLnInO.sub.x, CaLnAlSrO.sub.x and CaLnAlSrO.sub.x,
wherein Ln is a lanthanide or yttrium and x is number such that all
charges are balanced. For example, in some embodiments, the
catalytic nanowire comprises CaLaBO.sub.4, CaLaAlO.sub.4,
CaLaGaO.sub.4, CaLaInO.sub.4, CaLaAlSrO.sub.5, CaLaAlSrO.sub.5,
CaNdBO.sub.4, CaNdAlO.sub.4, CaNdGaO.sub.4, CaNdInO.sub.4,
CaNdAlSrO.sub.4, CaNdAlSrO.sub.4, CaYbBO.sub.4, CaYbAlO.sub.4,
CaYbGaO.sub.4, CaYbInO.sub.4, CaYbAlSrO.sub.5, CaYbAlSrO.sub.5,
CaEuBO.sub.4, CaEuAlO.sub.4, CaEuGaO.sub.4, CaEuInO.sub.4,
CaEuAlSrO.sub.5, CaEuAlSrO.sub.5, CaSmBO.sub.4, CaSmAlO.sub.4,
CaSmGaO.sub.4, CaSmInO.sub.4, CaSmAlSrO.sub.5, CaSmAlSrO.sub.5,
CaYBO.sub.4, CaYAlO.sub.4, CaYGaO.sub.4, CaYInO.sub.4,
CaYAlSrO.sub.5, CaYAlSrO.sub.5, CaCeBO.sub.4, CaCeAlO.sub.4,
CaCeGaO.sub.4, CaCeInO.sub.4, CaCeAlSrO.sub.5, CaCeAlSrO.sub.5,
CaPrBO.sub.4, CaPrAlO.sub.4, CaPrGaO.sub.4, CaPrInO.sub.4,
CaPrAlSrO.sub.5 or CaPrAlSrO.sub.5.
[0290] In still other embodiments, the invention is directed to a
catalytic nanowire comprising a rare earth oxide, wherein the
nanowires are doped with a dopant (or dopants) selected from Eu/Na,
Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm,
Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs,
K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm,
Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga,
Li/Na/Sr, Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La,
Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs,
Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm,
La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,
Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs,
Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs,
Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm,
Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb,
Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K,
Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,
Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs,
K/La/Zr/Ag, Lu/Fe, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga,
Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La,
Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Cs/La/Na, La/S/Sr, K/La/Zr/Ag,
Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu,
Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu,
Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta,
Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,
Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt,
Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr,
Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm, Sr/Pb, Sr/W/Li, Ca/Sr/W
or Sr/Hf. In one embodiment of the foregoing, nanowires comprise
La.sub.2O.sub.3, Nd.sub.2O.sub.3, Yb.sub.2O.sub.3, Eu.sub.2O.sub.3,
Sm.sub.2O.sub.3, Ln1.sub.4-xLn2.sub.xO.sub.6,
La.sub.4-xLn1.sub.xO.sub.6, La.sub.4-xNd.sub.xO.sub.6, wherein Ln1
and Ln2 are each independently a lanthanide element, wherein Ln1
and Ln2 are not the same and x is a number ranging from greater
than 0 to less than 4, La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6,
La.sub.1.5Nd.sub.2.5O.sub.6, La.sub.2.5Nd.sub.1.5O.sub.6,
La.sub.3.2Nd.sub.0.8O.sub.6, La.sub.3.5Nd.sub.0.5O.sub.6,
La.sub.3.8Nd.sub.0.2O.sub.6, Y--La, Zr--La, Pr--La or Ce--La or
combinations thereof.
[0291] In other embodiments, the nanowires comprise
La.sub.2O.sub.3, Yb.sub.2O.sub.3, Eu.sub.2O.sub.3, Sm.sub.2O.sub.3,
Y.sub.2O.sub.3, Ce.sub.2O.sub.3, Pr.sub.2O.sub.3,
Ln1.sub.4-xLn2.sub.xO.sub.6, La.sub.4-xLn1.sub.xO.sub.6,
La.sub.4-xNd.sub.xO.sub.6, wherein L.sub.n1 and L.sub.n2 are each
independently a lanthanide element, wherein L.sub.n1 and L.sub.n2
are not the same and x is a number ranging from greater than 0 to
less than 4, La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6,
La.sub.1.5Nd.sub.2.5O.sub.6, La.sub.2.5Nd.sub.1.5O.sub.6,
La.sub.3.2Nd.sub.0.8O.sub.6, La.sub.3.5Nd.sub.0.5O.sub.6,
La.sub.3.8Nd.sub.0.2O.sub.6, Y--La, Zr--La, Pr--La or Ce--La doped
with Sr/Ta, for example in some embodiments the nanowires comprise
Sr/Ta/La.sub.2O.sub.3, Sr/Ta/Yb.sub.2O.sub.3,
Sr/Ta/Eu.sub.2O.sub.3, Sr/Ta/Sm.sub.2O.sub.3,
Sr/Ta/La.sub.3NdO.sub.6, Sr/Ta/LaNd.sub.3O.sub.6,
Sr/Ta/La.sub.1.5Nd.sub.2.5O.sub.6,
Sr/Ta/La.sub.2.5Nd.sub.1.5O.sub.6,
Sr/Ta/La.sub.3.2Nd.sub.0.8O.sub.6,
Sr/Ta/La.sub.3.5Nd.sub.0.5O.sub.6,
Sr/Ta/La.sub.3.8Nd.sub.0.2O.sub.6, Sr/Ta/Y--La, Sr/Ta/Zr--La,
Sr/Ta/Pr--La or Sr/Ta/Ce--La or combinations thereof. In other
embodiments, the nanowires comprise Ln1.sub.4-xLn2.sub.xO.sub.6,
La.sub.4-xLn1.sub.xO.sub.6, La.sub.4-xNd.sub.xO.sub.6, wherein Ln1
and Ln2 are each independently a lanthanide element, wherein Ln1
and Ln2 are not the same and x is a number ranging from greater
than 0 to less than 4, La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6,
La.sub.1.5Nd.sub.2.5O.sub.6, La.sub.2.5Nd.sub.1.5O.sub.6,
La.sub.3.2Nd.sub.0.8O.sub.6, La.sub.3.5Nd.sub.0.5O.sub.6,
La.sub.3.8Nd.sub.0.2O.sub.6, Y--La, Zr--La, Pr--La or Ce--La doped
with Na, Sr, Ca, Yb, Cs or Sb, for example the nanowires may
comprise Na/Ln1.sub.4-xLn2.sub.xO.sub.6,
Sr/Ln1.sub.4-xLn2.sub.xO.sub.6, Ca/Ln1.sub.4-xLn2.sub.xO.sub.6,
Yb/Ln1.sub.4-xLn2.sub.xO.sub.6, Cs/Ln1.sub.4-xLn2.sub.xO.sub.6,
Sb/Ln1.sub.4-xLn2.sub.xO.sub.6, Na/La.sub.4-xLn1.sub.xO.sub.6,
Na/La.sub.3NdO.sub.6, Sr/La.sub.4-xLn1.sub.xO.sub.6,
Ca/La.sub.4-xLn1.sub.xO.sub.6, Yb/La.sub.4-xLn1.sub.xO.sub.6,
Cs/La.sub.4-xLn1.sub.xO.sub.6, Sb/La.sub.4-xLn1.sub.xO.sub.6,
Na/La.sub.4-xNd.sub.xO.sub.6, Sr/La.sub.4-xNd.sub.xO.sub.6,
Ca/La.sub.4-xNd.sub.xO.sub.6, Yb/La.sub.4-xNd.sub.xO.sub.6, Cs
La.sub.4-xNd.sub.xO.sub.6, Sb/La.sub.4-xNd.sub.xO.sub.6,
Na/LaNd.sub.3O.sub.6, Na/La.sub.1.5Nd.sub.2.5O.sub.6,
Na/La.sub.2.5Nd.sub.1.5O.sub.6, Na/La.sub.3.2Nd.sub.0.8O.sub.6,
Na/La.sub.3.5Nd.sub.0.5O.sub.6, Na/La.sub.3.8Nd.sub.0.2O.sub.6,
Na/Y--La, Na/Zr--La, Na/Pr--La, Na/Ce--La, Sr/La.sub.3NdO.sub.6,
Sr/LaNd.sub.3O.sub.6, Sr/La.sub.1.5Nd.sub.2.5O.sub.6,
Sr/La.sub.2.5Nd.sub.1.5O.sub.6, Sr/La.sub.3.2Nd.sub.0.8O.sub.6,
Sr/La.sub.3.5Nd.sub.0.5O.sub.6, Sr/La.sub.3.8Nd.sub.0.2O.sub.6,
Sr/Y--La, Sr/Zr--La, Sr/Pr--La, Sr/Ce--La, Ca/La.sub.3NdO.sub.6,
Ca/LaNd.sub.3O.sub.6, Ca/La.sub.1.5Nd.sub.2.5O.sub.6,
Ca/La.sub.2.5Nd.sub.1.5O.sub.6, Ca/La.sub.3.2Nd.sub.0.8O.sub.6,
Ca/La.sub.3.5Nd.sub.0.5O.sub.6, Ca/La.sub.3.8Nd.sub.0.2O.sub.6,
Ca/Y--La, Ca/Zr--La, Ca/Pr--La, Ca/Ce--La, Yb/La.sub.3NdO.sub.6,
Yb/LaNd.sub.3O.sub.6, Yb/La.sub.1.5Nd.sub.2.5O.sub.6,
Yb/La.sub.2.5Nd.sub.1.5O.sub.6, Yb/La.sub.3.2Nd.sub.0.8O.sub.6,
Yb/La.sub.3.5Nd.sub.0.5O.sub.6, Yb/La.sub.3.8Nd.sub.0.2O.sub.6,
Yb/Y--La, Yb/Zr--La, Yb/Pr--La, Yb/Ce--La,
Cs/La.sub.3NdO.sub.6LaNd.sub.3O.sub.6,
Cs/La.sub.1.5Nd.sub.2.5O.sub.6, Cs/La.sub.2.5Nd.sub.1.5O.sub.6,
Cs/La.sub.3.2Nd.sub.0.8O.sub.6, Cs/La.sub.3.5Nd.sub.0.5O.sub.6,
Cs/La.sub.3.8Nd.sub.0.2O.sub.6, Cs/Y--La, Cs/Zr--La, Cs/Pr--La,
Cs/Ce--La, Sb/La.sub.3NdO.sub.6, Sb/LaNd.sub.3O.sub.6,
Sb/La.sub.1.5Nd.sub.2.5O.sub.6, Sb/La.sub.2.5Nd.sub.1.5O.sub.6,
Sb/La.sub.3.2Nd.sub.0.8O.sub.6, Sb/La.sub.3.5Nd.sub.0.5O.sub.6,
Sb/La.sub.3.8Nd.sub.0.2O.sub.6, Sb/Y--La, Sb/Zr--La, Sb/Pr--La,
Sb/Ce--La or combinations thereof.
[0292] Furthermore, the present inventors have discovered that
lanthanide oxides doped with alkali metals and/or alkaline earth
metals and at least one other dopant selected from Groups 3-16 have
desirable catalytic properties and are useful in a variety of
catalytic reactions, such as OCM. Accordingly, in one embodiment
the nanowire catalysts comprise a lanthanide oxide doped with an
alkali metal, an alkaline earth metal or combinations thereof, and
at least one other dopant from groups 3-16. In some embodiments,
the nanowire catalyst comprises a lanthanide oxide, an alkali metal
dopant and at least one other dopant selected from Groups 3-16. In
other embodiments, the nanowire catalyst comprises a lanthanide
oxide, an alkaline earth metal dopant and at least one other dopant
selected from Groups 3-16.
[0293] In some more specific embodiments of the foregoing, the
nanowire catalyst comprises a lanthanide oxide, a lithium dopant
and at least one other dopant selected from Groups 3-16. In still
other embodiments, the nanowire catalyst comprises a lanthanide
oxide, a sodium dopant and at least one other dopant selected from
Groups 3-16. In other embodiments, the nanowire catalyst comprises
a lanthanide oxide, a potassium dopant and at least one other
dopant selected from Groups 3-16. In other embodiments, the
nanowire catalyst comprises a lanthanide oxide, a rubidium dopant
and at least one other dopant selected from Groups 3-16. In more
embodiments, the nanowire catalyst comprises a lanthanide oxide, a
caesium dopant and at least one other dopant selected from Groups
3-16.
[0294] In still other embodiments of the foregoing, the nanowire
catalyst comprises a lanthanide oxide, a beryllium dopant and at
least one other dopant selected from Groups 3-16. In other
embodiments, the nanowire catalyst comprises a lanthanide oxide, a
magnesium dopant and at least one other dopant selected from Groups
3-16. In still other embodiments, the nanowire catalyst comprises a
lanthanide oxide, a calcium dopant and at least one other dopant
selected from Groups 3-16. In more embodiments, the nanowire
catalyst comprises a lanthanide oxide, a strontium dopant and at
least one other dopant selected from Groups 3-16. In more
embodiments, the nanowire catalyst comprises a lanthanide oxide, a
barium dopant and at least one other dopant selected from Groups
3-16.
[0295] In some embodiments of the foregoing lanthanide oxide
nanowire catalysts, the catalysts comprise La.sub.2O.sub.3,
Nd.sub.2O.sub.3, Yb.sub.2O.sub.3, Eu.sub.2O.sub.3, Sm.sub.2O.sub.3,
Ln1.sub.4-xLn2.sub.xO.sub.6, La.sub.4-xLn1.sub.xO.sub.6,
La.sub.4-xNd.sub.xO.sub.6, wherein Ln1 and Ln2 are each
independently a lanthanide element, wherein Ln1 and Ln2 are not the
same and x is a number ranging from greater than 0 to less than 4,
La.sub.3NdO.sub.6, LaNd.sub.3O.sub.6, La.sub.1.5Nd.sub.2.5O.sub.6,
La.sub.2.5Nd.sub.1.5O.sub.6, La.sub.3.2Nd.sub.0.8O.sub.6,
La.sub.3.5Nd.sub.0.5O.sub.6, La.sub.3.8Nd.sub.0.2O.sub.6, Y--La,
Zr--La, Pr--La or Ce--La or combinations thereof. In other various
embodiments, the lanthanide oxide nanowire catalyst comprises a
C.sub.2 selectivity of greater than 50% and a methane conversion of
greater than 20% when the lanthanide oxide nanowire catalyst is
employed as a heterogenous catalyst in the oxidative coupling of
methane at a temperature of 750.degree. C. or less.
[0296] In various embodiments, of any of the above nanowire
catalysts, the nanowire catalyst comprises a C.sub.2 selectivity of
greater than 50% and a methane conversion of greater than 20% when
the nanowire catalyst is employed as a heterogenous catalyst in the
oxidative coupling of methane at a temperature of 750.degree. C. or
less, 700.degree. C. or less, 650.degree. C. or less or even
600.degree. C. or less.
[0297] In more embodiments, of any of the above nanowire catalysts,
the nanowire catalyst comprises a C.sub.2 selectivity of greater
than 50%, greater than 55%, greater than 60%, greater than 65%,
greater than 70%, or even greater than 75%, and a methane
conversion of greater than 20% when the nanowire catalyst is
employed as a heterogenous catalyst in the oxidative coupling of
methane at a temperature of 750.degree. C. or less.
[0298] In other embodiments, of any of the above catalysts, the
catalyst comprises a C.sub.2 selectivity of greater than 50%, and a
methane conversion of greater than 20%, greater than 25%, greater
than 30%, greater than 35%, greater than 40%, greater than 45%, or
even greater than 50% when the rare earth oxide catalyst is
employed as a heterogenous catalyst in the oxidative coupling of
methane at a temperature of 750.degree. C. or less. In some
embodiments of the foregoing, the methan conversion and C2
selectivity are calculated based on a single pass basis (i.e., the
percent of methane converted or C2 selectivity upon a single pass
over the catalyst or catalytic bed, etc.)
[0299] In some embodiments, the foregoing doped nanowires comprise
1, 2, 3 or four doping elements. In other embodiments, the
nanowires comprise more than four doping elements, for example, 5,
6, 7, 8, 9, 10 or even more doping elements. In this regard, each
dopant may be present in the nanowires (for example any of the
nanowires disclosed in Tables 9-12) in up to 75% by weight. For
example, in one embodiment the concentration of a first doping
element ranges from 0.01 to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20%
ww, 20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for example about 1%
w/w, about 2% w/w, about 3% w/w, about 4% w/w, about 5% w/w, about
6% w/w, about 7% w/w, about 8% w/w, about 9% w/w, about 10% w/w,
about 11% w/w, about 12% w/w, about 13% w/w, about 14% w/w, about
15% w/w, about 16% w/w, about 17% w/w, about 18% w/w, about 19% w/w
or about 20% w/w.
[0300] In other embodiments, the concentration of a second doping
element (when present) ranges from 0.01% to 1% w/w, 1%-5% w/w,
5%-10% w/w. 10%-20% ww, 20%-30% w/w, 30%-40% w/w or 40%-50% w/w,
for example about 1% w/w, about 2% w/w, about 3% w/w, about 4% w/w,
about 5% w/w, about 6% w/w, about 7% w/w, about 8% w/w, about 9%
w/w, about 10% w/w, about 11% w/w, about 12% w/w, about 13% w/w,
about 14% w/w, about 15% w/w, about 16% w/w, about 17% w/w, about
18% w/w, about 19% w/w or about 20% w/w.
[0301] In other embodiments, the concentration of a third doping
element (when present) ranges from 0.01% to 1% w/w, 1%-5% w/w,
5%-10% w/w. 10%-20% ww, 20%-30% w/w, 30%-40% w/w or 40%-50% w/w,
for example about 1% w/w, about 2% w/w, about 3% w/w, about 4% w/w,
about 5% w/w, about 6% w/w, about 7% w/w, about 8% w/w, about 9%
w/w, about 10% w/w, about 11% w/w, about 12% w/w, about 13% w/w,
about 14% w/w, about 15% w/w, about 16% w/w, about 17% w/w, about
18% w/w, about 19% w/w or about 20% w/w. In other embodiments, the
concentration of a fourth doping element (when present) ranges from
0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww, 20%-30% w/w,
30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about 2% w/w,
about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7%
w/w, about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w,
about 12% w/w, about 13% w/w, about 14% w/w, about 15% w/w, about
16% w/w, about 17% w/w, about 18% w/w, about 19% w/w or about 20%
w/w.
[0302] In other embodiments, the concentration of the dopant is
measured in terms of atomic percent (at/at). In some of these
embodiments, each dopant may be present in the nanowires (for
example any of the nanowires disclosed in Tables 1-12) in up to 75%
at/at. For example, in one embodiment the concentration of a first
doping element ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10%
at/at. 10%-20% at/at, 20%-30% at/at, 30%-40% at/at or 40%-50%
at/at, for example about 1% at/at, about 2% at/at, about 3% at/at,
about 4% at/at, about 5% at/at, about 6% at/at, about 7% at/at,
about 8% at/at, about 9% at/at, about 10% at/at, about 11% at/at,
about 12% at/at, about 13% at/at, about 14% at/at, about 15% at/at,
about 16% at/at, about 17% at/at, about 18% at/at, about 19% at/at
or about 20% at/at.
[0303] In other embodiments, the concentration of a second doping
element (when present) ranges from 0.01% to 1% at/at, 1%-5% at/at,
5%-10% at/at. 10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50%
at/at, for example about 1% at/at, about 2% at/at, about 3% at/at,
about 4% at/at, about 5% at/at, about 6% at/at, about 7% at/at,
about 8% at/at, about 9% at/at, about 10% at/at, about 11% at/at,
about 12% at/at, about 13% at/at, about 14% at/at, about 15% at/at,
about 16% at/at, about 17% at/at, about 18% at/at, about 19% at/at
or about 20% at/at.
[0304] In other embodiments, the concentration of a third doping
element (when present) ranges from 0.01% to 1% at/at, 1%-5% at/at,
5%-10% at/at. 10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50%
at/at, for example about 1% at/at, about 2% at/at, about 3% at/at,
about 4% at/at, about 5% at/at, about 6% at/at, about 7% at/at,
about 8% at/at, about 9% at/at, about 10% at/at, about 11% at/at,
about 12% at/at, about 13% at/at, about 14% at/at, about 15% at/at,
about 16% at/at, about 17% at/at, about 18% at/at, about 19% at/at
or about 20% at/at.
[0305] In other embodiments, the concentration of a fourth doping
element (when present) ranges from 0.01% to 1% at/at, 1%-5% at/at,
5%-10% at/at. 10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50%
at/at, for example about 1% at/at, about 2% at/at, about 3% at/at,
about 4% at/at, about 5% at/at, about 6% at/at, about 7% at/at,
about 8% at/at, about 9% at/at, about 10% at/at, about 11% at/at,
about 12% at/at, about 13% at/at, about 14% at/at, about 15% at/at,
about 16% at/at, about 17% at/at, about 18% at/at, about 19% at/at
or about 20% at/at.
[0306] Accordingly, any of the doped nanowires described above or
in Tables 1-12, may comprise any of the foregoing doping
concentrations.
[0307] Furthermore, different catalytic characteristics of the
above doped nanowires can be varied or "tuned" based on the method
used to prepare them. For example, in one embodiment the above
nanowires (and the nanowires of Tables 1-12) are prepared using a
biological templating approach, for example phage. In other
embodiments, the nanowires are prepared via a hydrothermal or sol
gel approach (i.e., a non-templated approach). Some embodiments for
preparing the nanowires (e.g., rare earth nanowires) comprise
preparing the nanowires directly from the corresponding oxide or
via a metal hydroxide gel approach. Such methods are described in
more detail herein and other methods are known in the art. In
addition, the above dopants may be incorporated either before or
after (or combinations thereof) an optional calcincation step as
described herein.
[0308] In other embodiments, the nanowires comprise a mixed oxide
selected from a Y--La mixed oxide doped with Na. (Y ranges from 5
to 20% of La mol/mol); a Zr--La mixed oxide doped with Na (Zr
ranges from 1 to 5% of La mo/mol); a Pr--La mixed oxide doped with
a group 1 element (Pr ranges from 2 to 6% of La mol/mol); and a
Ce--La mixed oxide doped with a group 1 element (Ce ranges from 5
to 20% of La mol/mol). As used herein, the notation "M1-M2",
wherein M1 and M2 are each independently metals refers to a mixed
metal oxide comprising the two metals. M1 and M2 may be present in
equal or different amounts (at/at).
[0309] Some embodiments of the metal oxides disclosed herein can be
in the form of oxides, oxyhydroxides, hydroxides, oxycarbonates or
combination thereof after being exposed to moisture, carbon
dioxide, undergoing incomplete calcination or combination
thereof.
[0310] It is contemplated that any one or more of the dopants
disclosed herein can be combined with any one of the nanowires
disclosed herein to form a doped nanowire comprising one, two,
three or more dopants. Tables 1-12 below show exemplary doped
nanowires in accordance with various specific embodiments. Dopants
(Dop) are shown in the horizontal rows and base nanowire catalyst
(NW) in the vertical columns for Tables 1-8, and dopants are shown
in the vertical columns and base nanowire catalyst in the
horizontal rows for Tables 9-12. The resulting doped catalysts are
shown in the intersecting cells in all tables. In some embodiments,
the doped nanowires shown in tables 1-12 are doped with one, two,
three or more additional dopants.
TABLE-US-00001 TABLE 1 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Li Na K Rb Li.sub.2O Li/ Na/ K/ Rb/ Li.sub.2O
Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O Li/ Na/ K/ Rb/ Na.sub.2O
Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O Li/ Na/ K/ Rb/ K.sub.2O
K.sub.2O K.sub.2O K.sub.2O Rb.sub.2O Li/ Na/ K/ Rb/ Rb.sub.2O
Rb.sub.2O Rb.sub.2O Rb.sub.2O Cs.sub.2O Li/ Na/ K/ Rb/ Cs.sub.2O
Cs.sub.2O Cs.sub.2O Cs.sub.2O BeO Li/ Na/ K/ Rb/ BeO BeO BeO BeO
MgO Li/ Na/ K/ Rb/ MgO MgO MgO MgO CaO Li/ Na/ K/ Rb/ CaO CaO CaO
CaO SrO Li/ Na/ K/ Rb/ SrO SrO SrO SrO BaO Li/ Na/ K/ Rb/ BaO BaO
BaO BaO Sc.sub.2O.sub.3 Li/ Na/ K/ Rb/ Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Li/
Na/ K/ Rb/ Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 La.sub.2O.sub.3 Li/ Na/ K/ Rb/ La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Li/ Na/
K/ Rb/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Li/
Na/ K/ Rb/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Li/ Na/ K/ Rb/ Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Li/
Na/ K/ Rb/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Li/ Na/ K/ Rb/ Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Li/
Na/ K/ Rb/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Li/ Na/ K/ Rb/ Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Li/
Na/ K/ Rb/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 TbO.sub.2 Li/ Na/ K/ Rb/ TbO.sub.2 TbO.sub.2
TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Li/ Na/ K/ Rb/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Li/ Na/ K/ Rb/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Li/ Na/ K/ Rb/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Li/ Na/ K/ Rb/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Li/ Na/ K/ Rb/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Li/ Na/ K/ Rb/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Li/ Na/ K/ Rb/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Li/ Na/ K/ Rb/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Li/ Na/ K/ Rb/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Li/ Na/ K/ Rb/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Li/ Na/ K/ Rb/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Li/ Na/ K/ Rb/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Li/ Na/ K/ Rb/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Li/ Na/ K/ Rb/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Li/ Na/ K/ Rb/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Li/ Na/ K/ Rb/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Li/ Na/ K/ Rb/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Li/ Na/ K/ Rb/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Li/ Na/ K/ Rb/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Li/ Na/ K/ Rb/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Li/ Na/ K/ Rb/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Li/ Na/ K/ Rb/ VO VO VO VO
V.sub.2O.sub.3 Li/ Na/ K/ Rb/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Li/ Na/ K/ Rb/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Li/ Na/ K/ Rb/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Li/ Na/ K/ Rb/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Li/ Na/ K/ Rb/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Li/ Na/ K/ Rb/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Li/ Na/ K/ Rb/ NbO NbO NbO NbO
NbO.sub.2 Li/ Na/ K/ Rb/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Li/ Na/ K/ Rb/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Li/ Na/ K/ Rb/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Li/ Na/ K/ Rb/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Li/ Na/ K/ Rb/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Li/ Na/ K/ Rb/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Li/ Na/ K/ Rb/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Li/ Na/ K/ Rb/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Li/ Na/ K/ Rb/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Li/ Na/ K/ Rb/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Li/ Na/ K/ Rb/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Li/ Na/ K/ Rb/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Li/ Na/ K/ Rb/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Li/ Na/ K/ Rb/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Li/ Na/ K/ Rb/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Li/ Na/ K/ Rb/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Li/ Na/ K/ Rb/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Li/ Na/ K/ Rb/ MnO MnO MnO MnO
Mn/Mg/O Li/ Na/ K/ Rb/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Li/ Na/ K/ Rb/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Li/ Na/ K/ Rb/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Li/ Na/ K/ Rb/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Li/ Na/ K/ Rb/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Li/ Na/ K/ Rb/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Li/ Na/ K/ Rb/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Li/ Na/ K/ Rb/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Li/ Na/ K/ Rb/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Li/ Na/ K/ Rb/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Li/ Na/ K/ Rb/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Li/ Na/ K/ Rb/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8 Li/ Na/ K/ Rb/
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8 Mn.sub.2O.sub.4
Li/ Na/ K/ Rb/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Na.sub.4P.sub.2O.sub.7 Li/ Na/ K/ Rb/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Li/
Na/ K/ Rb/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/ Li/ Na/ K/ Rb/ WO.sub.4
Mn.sub.3O.sub.4/ Mn.sub.3O.sub.4/ Mn.sub.3O.sub.4/ Mn.sub.3O.sub.4/
WO.sub.4 WO.sub.4 WO.sub.4 WO.sub.4 Na.sub.2WO.sub.4 Li/ Na/ K/ Rb/
Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Zr.sub.2Mo.sub.2O.sub.8 Li/ Na/ K/ Rb/ Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Li/ Na/ K/ Rb/ MgO
NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/ MgO MgO
MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Li/ Na/ K/ Rb/
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Li/ Na/ K/ Rb/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Li/ Na/ K/ Rb/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Li/ Na/ K/ Rb/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Li/ Na/ K/ Rb/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Li/ Na/ K/ Rb/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Li/ Na/ K/ Rb/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Li/ Na/ K/ Rb/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Li/
Na/ K/ Rb/ Y--La Y--La Y--La Y--La Zr--La Li/ Na/ K/ Rb/ Zr--La
Zr--La Zr--La Zr--La Pr--La Li/ Na/ K/ Rb/ Pr--La Pr--La Pr--La
Pr--La Ce--La Li/ Na/ K/ Rb/ Ce--La Ce--La Ce--La Ce--La Dop NW Cs
Be Mg Ca Li.sub.2O Cs/ Be/ Mg/ Ca/ Li.sub.2O Li.sub.2O Li.sub.2O
Li.sub.2O Na.sub.2O Cs/ Be/ Mg/ Ca/ Na.sub.2O Na.sub.2O Na.sub.2O
Na.sub.2O K.sub.2O Cs/ Be/ Mg/ Ca/ K.sub.2O K.sub.2O K.sub.2O
K.sub.2O Rb.sub.2O Cs/ Be/ Mg/ Ca/ Rb.sub.2O Rb.sub.2O Rb.sub.2O
Rb.sub.2O Cs.sub.2O Cs/ Be/ Mg/ Ca/ Cs.sub.2O Cs.sub.2O Cs.sub.2O
Cs.sub.2O BeO Cs/ Be/ Mg/ Ca/ BeO BeO BeO BeO MgO Cs/ Be/ Mg/ Ca/
MgO MgO MgO MgO CaO Cs/ Be/ Mg/ Ca/ CaO CaO CaO CaO SrO Cs/ Be/ Mg/
Ca/ SrO SrO SrO SrO BaO Cs/ Be/ Mg/ Ca/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Y.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3
CeO.sub.2 Cs/ Be/ Mg/ Ca/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2
Ce.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Eu.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2 Cs/ Be/ Mg/ Ca/ TbO.sub.2
TbO.sub.2 TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Cs/ Be/ Mg/ Ca/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Cs/ Be/ Mg/ Ca/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Cs/ Be/ Mg/ Ca/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Cs/ Be/ Mg/ Ca/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Cs/ Be/ Mg/ Ca/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Cs/ Be/ Mg/ Ca/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Cs/ Be/ Mg/ Ca/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Cs/ Be/ Mg/ Ca/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Cs/ Be/ Mg/ Ca/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Cs/ Be/ Mg/ Ca/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Cs/ Be/ Mg/ Ca/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Cs/ Be/ Mg/ Ca/ VO VO VO VO
V.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Cs/ Be/ Mg/ Ca/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Cs/ Be/ Mg/ Ca/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Cs/ Be/ Mg/ Ca/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Cs/ Be/ Mg/ Ca/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Cs/ Be/ Mg/ Ca/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Cs/ Be/ Mg/ Ca/ NbO NbO NbO NbO
NbO.sub.2 Cs/ Be/ Mg/ Ca/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Cs/ Be/ Mg/ Ca/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Cs/ Be/ Mg/ Ca/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Cs/ Be/ Mg/ Ca/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Cs/ Be/ Mg/ Ca/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Cs/ Be/ Mg/ Ca/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Cs/ Be/ Mg/ Ca/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Cs/ Be/ Mg/ Ca/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Cs/ Be/ Mg/ Ca/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Cs/ Be/ Mg/ Ca/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Cs/ Be/ Mg/ Ca/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Cs/ Be/ Mg/ Ca/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Cs/ Be/ Mg/ Ca/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Cs/ Be/ Mg/ Ca/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Cs/ Be/ Mg/ Ca/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Cs/ Be/ Mg/ Ca/ MnO MnO MnO MnO
Mn/Mg/O Cs/ Be/ Mg/ Ca/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Cs/ Be/ Mg/ Ca/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Cs/ Be/ Mg/ Ca/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Cs/ Be/ Mg/ Ca/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Cs/ Be/ Mg/ Ca/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Cs/ Be/ Mg/ Ca/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Cs/ Be/ Mg/ Ca/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Cs/ Be/ Mg/ Ca/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Cs/ Be/ Mg/ Ca/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Cs/ Be/ Mg/ Ca/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Cs/ Be/ Mg/ Ca/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Cs/ Be/ Mg/ Ca/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8 Cs/ Be/ Mg/ Ca/
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8 Mn.sub.2O.sub.4
Cs/ Be/ Mg/ Ca/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Na.sub.4P.sub.2O.sub.7 Cs/ Be/ Mg/ Ca/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Cs/
Be/ Mg/ Ca/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/ Cs/ Be/ Mg/ Ca/ WO.sub.4
Mn.sub.3O.sub.4/ Mn.sub.3O.sub.4/ Mn.sub.3O.sub.4/ Mn.sub.3O.sub.4/
WO.sub.4 WO.sub.4 WO.sub.4 WO.sub.4 Na.sub.2WO.sub.4 Cs/ Be/ Mg/
Ca/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Cs/ Be/ Mg/ Ca/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Cs/
Be/ Mg/ Ca/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Cs/ Be/
Mg/ Ca/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Cs/ Be/ Mg/ Ca/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Cs/ Be/ Mg/ Ca/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Cs/ Be/ Mg/ Ca/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Cs/ Be/ Mg/ Ca/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Cs/ Be/ Mg/ Ca/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Cs/ Be/ Mg/ Ca/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Cs/ Be/ Mg/ Ca/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Cs/
Be/ Mg/ Ca/ Y--La Y--La Y--La Y--La Zr--La Cs/ Be/ Mg/ Ca/ Zr--La
Zr--La Zr--La Zr--La Pr--La Cs/ Be/ Mg/ Ca/ Pr--La Pr--La Pr--La
Pr--La Ce--La Cs/ Be/ Mg/ Ca/ Ce--La Ce--La Ce--La Ce--La
TABLE-US-00002 TABLE 2 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Sr Ba B P Li.sub.2O Sr/ Ba/ B/ P/ Li.sub.2O Li.sub.2O
Li.sub.2O Li.sub.2O Na.sub.2O Sr/ Ba/ B/ P/ Na.sub.2O Na.sub.2O
Na.sub.2O Na.sub.2O K.sub.2O Sr/ Ba/ B/ P/ K.sub.2O K.sub.2O
K.sub.2O K.sub.2O Rb.sub.2O Sr/ Ba/ B/ P/ Rb.sub.2O Rb.sub.2O
Rb.sub.2O Rb.sub.2O Cs.sub.2O Sr/ Ba/ B/ P/ Cs.sub.2O Cs.sub.2O
Cs.sub.2O Cs.sub.2O BeO Sr/ Ba/ B/ P/ BeO BeO BeO BeO MgO Sr/ Ba/
B/ P/ MgO MgO MgO MgO CaO Sr/ Ba/ B/ P/ CaO CaO CaO CaO SrO Sr/ Ba/
B/ P/ SrO SrO SrO SrO BaO Sr/ Ba/ B/ P/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Sr/ Ba/ B/ P/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Sr/ Ba/ B/ P/
Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
La.sub.2O.sub.3 Sr/ Ba/ B/ P/ La.sub.2O.sub.3 La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Sr/ Ba/ B/ P/ CeO.sub.2
CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Sr/ Ba/ B/ P/
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Pr.sub.2O.sub.3 Sr/ Ba/ B/ P/ Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Sr/ Ba/ B/ P/
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Sm.sub.2O.sub.3 Sr/ Ba/ B/ P/ Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Sr/ Ba/ B/ P/
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Gd.sub.2O.sub.3 Sr/ Ba/ B/ P/ Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Sr/ Ba/ B/ P/
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
TbO.sub.2 Sr/ Ba/ B/ P/ TbO.sub.2 TbO.sub.2 TbO.sub.2 TbO.sub.2
Tb.sub.6O.sub.11 Sr/ Ba/ B/ P/ Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Dy.sub.2O.sub.3 Sr/ Ba/ B/ P/
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Ho.sub.2O.sub.3 Sr/ Ba/ B/ P/ Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Er.sub.2O.sub.3 Sr/ Ba/ B/ P/
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Er.sub.2O.sub.3 Er.sub.2O.sub.3
Tm.sub.2O.sub.3 Sr/ Ba/ B/ P/ Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Yb.sub.2O.sub.3 Sr/ Ba/ B/ P/
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Lu.sub.2O.sub.3 Sr/ Ba/ B/ P/ Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Ac.sub.2O.sub.3 Sr/ Ba/ B/ P/
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Th.sub.2O.sub.3 Sr/ Ba/ B/ P/ Th.sub.2O.sub.3 Th.sub.2O.sub.3
Th.sub.2O.sub.3 Th.sub.2O.sub.3 ThO.sub.2 Sr/ Ba/ B/ P/ ThO.sub.2
ThO.sub.2 ThO.sub.2 ThO.sub.2 Pa.sub.2O.sub.3 Sr/ Ba/ B/ P/
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
PaO.sub.2 Sr/ Ba/ B/ P/ PaO.sub.2 PaO.sub.2 PaO.sub.2 PaO.sub.2
TiO.sub.2 Sr/ Ba/ B/ P/ TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO
Sr/ Ba/ B/ P/ TiO TiO TiO TiO Ti.sub.2O.sub.3 Sr/ Ba/ B/ P/
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.3O Sr/ Ba/ B/ P/ Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.3O
Ti.sub.2O Sr/ Ba/ B/ P/ Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.2O
Ti.sub.3O.sub.5 Sr/ Ba/ B/ P/ Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.4O.sub.7 Sr/ Ba/ B/ P/
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
ZrO.sub.2 Sr/ Ba/ B/ P/ ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2
HfO.sub.2 Sr/ Ba/ B/ P/ HfO.sub.2 HfO.sub.2 HfO.sub.2 HfO.sub.2 VO
Sr/ Ba/ B/ P/ VO VO VO VO V.sub.2O.sub.3 Sr/ Ba/ B/ P/
V.sub.2O.sub.3 V.sub.2O.sub.3 V.sub.2O.sub.3 V.sub.2O.sub.3
VO.sub.2 Sr/ Ba/ B/ P/ VO.sub.2 VO.sub.2 VO.sub.2 VO.sub.2
V.sub.2O.sub.5 Sr/ Ba/ B/ P/ V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.3O.sub.7 Sr/ Ba/ B/ P/
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.4O.sub.9 Sr/ Ba/ B/ P/ V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.6O.sub.13 Sr/ Ba/ B/ P/
V.sub.6O.sub.13 V.sub.6O.sub.13 V.sub.6O.sub.13 V.sub.6O.sub.13 NbO
Sr/ Ba/ B/ P/ NbO NbO NbO NbO NbO.sub.2 Sr/ Ba/ B/ P/ NbO.sub.2
NbO.sub.2 NbO.sub.2 NbO.sub.2 Nb.sub.2O.sub.5 Sr/ Ba/ B/ P/
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.8O.sub.19 Sr/ Ba/ B/ P/ Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.16O.sub.38 Sr/ Ba/ B/ P/
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.12O.sub.29 Sr/ Ba/ B/ P/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Sr/ Ba/ B/ P/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Sr/ Ba/ B/ P/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Sr/ Ba/ B/ P/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Sr/ Ba/ B/ P/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Sr/ Ba/ B/ P/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Sr/ Ba/ B/ P/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Sr/ Ba/ B/ P/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Sr/ Ba/ B/ P/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Sr/ Ba/ B/ P/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Sr/ Ba/ B/ P/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Sr/ Ba/ B/ P/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Sr/ Ba/ B/ P/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Sr/ Ba/ B/ P/ MnO MnO MnO MnO
Mn/Mg/O Sr/ Ba/ B/ P/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Sr/ Ba/ B/ P/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Sr/ Ba/ B/ P/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Sr/ Ba/ B/ P/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Sr/ Ba/ B/ P/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Sr/ Ba/ B/ P/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Sr/ Ba/ B/ P/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Sr/ Ba/ B/ P/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Sr/ Ba/ B/ P/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Sr/ Ba/ B/ P/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Sr/ Ba/ B/ P/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Sr/ Ba/ B/ P/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8 Sr/ Ba/ B/ P/
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8 Mn.sub.2O.sub.4 Sr/
Ba/ B/ P/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Na.sub.4P.sub.2O.sub.7 Sr/ Ba/ B/ P/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Sr/
Ba/ B/ P/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Sr/ Ba/ B/ P/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Sr/ Ba/ B/ P/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Sr/ Ba/ B/ P/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4/MgO Sr/
Ba/ B/ P/ NaMnO.sub.4/MgO NaMnO.sub.4/MgO NaMnO.sub.4/MgO
NaMnO.sub.4/MgO Na.sub.10Mn--W.sub.5O.sub.17 Sr/ Ba/ B/ P/
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Sr/ Ba/ B/ P/ La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 LaNd.sub.3O.sub.6 Sr/ Ba/ B/ P/
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6 Sr/ Ba/ B/ P/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Sr/ Ba/ B/ P/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Sr/ Ba/ B/ P/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Sr/ Ba/ B/ P/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Sr/ Ba/ B/ P/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Sr/
Ba/ B/ P/ Y--La Y--La Y--La Y--La Zr--La Sr/ Ba/ B/ P/ Zr--La
Zr--La Zr--La Zr--La Pr--La Sr/ Ba/ B/ P/ Pr--La Pr--La Pr--La
Pr--La Ce--La Sr/ Ba/ B/ P/ Ce--La Ce--La Ce--La Ce--La Dop NW S F
Cl Li.sub.2O S/ F/ Cl/ Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O S/
F/ Cl/ Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O S/ F/ Cl/ K.sub.2O
K.sub.2O K.sub.2O Rb.sub.2O S/ F/ Cl/ Rb.sub.2O Rb.sub.2O Rb.sub.2O
Cs.sub.2O S/ F/ Cl/ Cs.sub.2O Cs.sub.2O Cs.sub.2O BeO S/ F/ Cl/ BeO
BeO BeO MgO S/ F/ Cl/ MgO MgO MgO CaO S/ F/ Cl/ CaO CaO CaO SrO S/
F/ Cl/ SrO SrO SrO BaO S/ F/ Cl/ BaO BaO BaO Sc.sub.2O.sub.3 S/ F/
Cl/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3
S/ F/ Cl/
Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 S/ F/
Cl/ La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 S/ F/
Cl/ CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 S/ F/ Cl/
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 S/
F/ Cl/ Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 S/ F/ Cl/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 S/ F/ Cl/ Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 S/ F/ Cl/
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 S/
F/ Cl/ Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 S/ F/ Cl/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 TbO.sub.2 S/ F/ Cl/ TbO.sub.2 TbO.sub.2 TbO.sub.2
Tb.sub.6O.sub.11 S/ F/ Cl/ Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Tb.sub.6O.sub.11 Dy.sub.2O.sub.3 S/ F/ Cl/ Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 S/ F/ Cl/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Er.sub.2O.sub.3 S/
F/ Cl/ Er.sub.2O.sub.3 Er.sub.2O.sub.3 Er.sub.2O.sub.3
Tm.sub.2O.sub.3 S/ F/ Cl/ Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Tm.sub.2O.sub.3 Yb.sub.2O.sub.3 S/ F/ Cl/ Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 S/ F/ Cl/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Ac.sub.2O.sub.3 S/
F/ Cl/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Th.sub.2O.sub.3 S/ F/ Cl/ Th.sub.2O.sub.3 Th.sub.2O.sub.3
Th.sub.2O.sub.3 ThO.sub.2 S/ F/ Cl/ ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 S/ F/ Cl/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 PaO.sub.2 S/ F/ Cl/ PaO.sub.2 PaO.sub.2 PaO.sub.2
TiO.sub.2 S/ F/ Cl/ TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO S/ F/ Cl/ TiO
TiO TiO Ti.sub.2O.sub.3 S/ F/ Cl/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.3O S/ F/ Cl/ Ti.sub.3O Ti.sub.3O Ti.sub.3O
Ti.sub.2O S/ F/ Cl/ Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5
S/ F/ Cl/ Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 S/ F/ Cl/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 ZrO.sub.2 S/ F/ Cl/ ZrO.sub.2 ZrO.sub.2 ZrO.sub.2
HfO.sub.2 S/ F/ Cl/ HfO.sub.2 HfO.sub.2 HfO.sub.2 VO S/ F/ Cl/ VO
VO VO V.sub.2O.sub.3 S/ F/ Cl/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 VO.sub.2 S/ F/ Cl/ VO.sub.2 VO.sub.2 VO.sub.2
V.sub.2O.sub.5 S/ F/ Cl/ V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.2O.sub.5 V.sub.3O.sub.7 S/ F/ Cl/ V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 S/ F/ Cl/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.6O.sub.13 S/ F/
Cl/ V.sub.6O.sub.13 V.sub.6O.sub.13 V.sub.6O.sub.13 NbO S/ F/ Cl/
NbO NbO NbO NbO.sub.2 S/ F/ Cl/ NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 S/ F/ Cl/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 S/ F/ Cl/ Nb.sub.8O.sub.19
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.16O.sub.38 S/ F/ Cl/
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 S/ F/ Cl/ Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.47O.sub.116 S/ F/ Cl/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Ta.sub.2O.sub.5 S/ F/ Cl/
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO S/ F/ Cl/ CrO
CrO CrO Cr.sub.2O.sub.3 S/ F/ Cl/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 CrO.sub.2 S/ F/ Cl/ CrO.sub.2 CrO.sub.2 CrO.sub.2
CrO.sub.3 S/ F/ Cl/ CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21
S/ F/ Cl/ Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 S/ F/ Cl/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.3 S/ F/
Cl/ MoO.sub.3 MoO.sub.3 MoO.sub.3 W.sub.2O.sub.3 S/ F/ Cl/
W.sub.2O.sub.3 W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 S/ F/ Cl/
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 S/ F/ Cl/ WoO.sub.3
WoO.sub.3 WoO.sub.3 MnO S/ F/ Cl/ MnO MnO MnO Mn/Mg/O S/ F/ Cl/
Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn.sub.3O.sub.4 S/ F/ Cl/ Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 S/ F/ Cl/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 MnO.sub.2 S/ F/ Cl/
MnO.sub.2 MnO.sub.2 MnO.sub.2 Mn.sub.2O.sub.7 S/ F/ Cl/
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 S/ F/ Cl/
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 S/ F/ Cl/ ReO.sub.3
ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 S/ F/ Cl/ Re.sub.2O.sub.7
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
S/ F/ Cl/ Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 S/ F/ Cl/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 S/ F/
Cl/ NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 S/ F/ Cl/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 S/ F/ Cl/ (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8 Mn.sub.2O.sub.4 S/ F/
Cl/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Na.sub.4P.sub.2O.sub.7 S/ F/ Cl/ Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 S/ F/
Cl/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mn.sub.3O.sub.4/WO.sub.4 S/ F/ Cl/ Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
S/ F/ Cl/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Zr.sub.2Mo.sub.2O.sub.8 S/ F/ Cl/ Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4/MgO S/
F/ Cl/ NaMnO.sub.4/MgO NaMnO.sub.4/MgO NaMnO.sub.4/MgO
Na.sub.10Mn--W.sub.5O.sub.17 S/ F/ Cl/ Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 S/ F/ Cl/ La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 LaNd.sub.3O.sub.6 S/ F/ Cl/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6 S/
F/ Cl/ La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6 S/ F/ Cl/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6 S/ F/ Cl/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6 S/ F/ Cl/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 S/ F/ Cl/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Y--La S/ F/ Cl/ Y--La Y--La Y--La
Zr--La S/ F/ Cl/ Zr--La Zr--La Zr--La Pr--La S/ F/ Cl/ Pr--La
Pr--La Pr--La Ce--La S/ F/ Cl/ Ce--La Ce--La Ce--La
TABLE-US-00003 TABLE 3 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW La Ce Pr Nd Li.sub.2O La/ Ce/ Pr/ Nd/ Li.sub.2O
Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O La/ Ce/ Pr/ Nd/ Na.sub.2O
Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O La/ Ce/ Pr/ Nd/ K.sub.2O
K.sub.2O K.sub.2O K.sub.2O Rb.sub.2O La/ Ce/ Pr/ Nd/ Rb.sub.2O
Rb.sub.2O Rb.sub.2O Rb.sub.2O Cs.sub.2O La/ Ce/ Pr/ Nd/ Cs.sub.2O
Cs.sub.2O Cs.sub.2O Cs.sub.2O BeO La/ Ce/ Pr/ Nd/ BeO BeO BeO BeO
MgO La/ Ce/ Pr/ Nd/ MgO MgO MgO MgO CaO La/ Ce/ Pr/ Nd/ CaO CaO CaO
CaO SrO La/ Ce/ Pr/ Nd/ SrO SrO SrO SrO BaO La/ Ce/ Pr/ Nd/ BaO BaO
BaO BaO Sc.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 La/
Ce/ Pr/ Nd/ Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 La.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 La/ Ce/
Pr/ Nd/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 La/
Ce/ Pr/ Nd/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 La/
Ce/ Pr/ Nd/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 La/
Ce/ Pr/ Nd/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 La/
Ce/ Pr/ Nd/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 TbO.sub.2 La/ Ce/ Pr/ Nd/ TbO.sub.2 TbO.sub.2
TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 La/ Ce/ Pr/ Nd/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 La/ Ce/ Pr/ Nd/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 La/ Ce/ Pr/ Nd/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 La/ Ce/ Pr/ Nd/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 La/ Ce/ Pr/ Nd/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 La/ Ce/ Pr/ Nd/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 La/ Ce/ Pr/ Nd/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 La/ Ce/ Pr/ Nd/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO La/ Ce/ Pr/ Nd/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O La/ Ce/ Pr/ Nd/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O La/ Ce/ Pr/ Nd/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 La/ Ce/ Pr/ Nd/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 La/ Ce/ Pr/ Nd/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 La/ Ce/ Pr/ Nd/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 La/ Ce/ Pr/ Nd/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO La/ Ce/ Pr/ Nd/ VO VO VO VO
V.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 La/ Ce/ Pr/ Nd/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 La/ Ce/ Pr/ Nd/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 La/ Ce/ Pr/ Nd/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 La/ Ce/ Pr/ Nd/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 La/ Ce/ Pr/ Nd/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO La/ Ce/ Pr/ Nd/ NbO NbO NbO NbO
NbO.sub.2 La/ Ce/ Pr/ Nd/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 La/ Ce/ Pr/ Nd/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 La/ Ce/ Pr/ Nd/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 La/ Ce/ Pr/ Nd/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 La/ Ce/ Pr/ Nd/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 La/ Ce/ Pr/ Nd/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 La/ Ce/ Pr/ Nd/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO La/ Ce/ Pr/ Nd/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 La/ Ce/ Pr/ Nd/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 La/ Ce/ Pr/ Nd/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 La/ Ce/ Pr/ Nd/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 La/ Ce/ Pr/ Nd/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 La/ Ce/ Pr/ Nd/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 La/ Ce/ Pr/ Nd/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 La/ Ce/ Pr/ Nd/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 La/ Ce/ Pr/ Nd/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO La/ Ce/ Pr/ Nd/ MnO MnO MnO MnO
Mn/Mg/O La/ Ce/ Pr/ Nd/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 La/ Ce/ Pr/ Nd/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 La/ Ce/ Pr/ Nd/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 La/ Ce/ Pr/ Nd/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 La/ Ce/ Pr/ Nd/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 La/ Ce/ Pr/ Nd/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 La/ Ce/ Pr/ Nd/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 La/ Ce/ Pr/ Nd/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 La/ Ce/ Pr/ Nd/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 La/ Ce/ Pr/ Nd/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 La/ Ce/ Pr/ Nd/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 La/ Ce/ Pr/ Nd/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8 La/ Ce/ Pr/ Nd/
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8 Mn.sub.2O.sub.4 La/
Ce/ Pr/ Nd/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Na.sub.4P.sub.2O.sub.7 La/ Ce/ Pr/ Nd/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 La/
Ce/ Pr/ Nd/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 La/ Ce/ Pr/ Nd/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
La/ Ce/ Pr/ Nd/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 La/ Ce/ Pr/ Nd/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ La/
Ce/ Pr/ Nd/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 La/ Ce/
Pr/ Nd/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 La/ Ce/ Pr/ Nd/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 La/ Ce/ Pr/ Nd/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La/ Ce/ Pr/ Nd/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La/ Ce/ Pr/ Nd/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La/ Ce/ Pr/ Nd/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La/ Ce/ Pr/ Nd/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La/ Ce/ Pr/ Nd/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La La/
Ce/ Pr/ Nd/ Y--La Y--La Y--La Y--La Zr--La La/ Ce/ Pr/ Nd/ Zr--La
Zr--La Zr--La Zr--La Pr--La La/ Ce/ Pr/ Nd/ Pr--La Pr--La Pr--La
Pr--La Ce--La La/ Ce/ Pr/ Nd/ Ce--La Ce--La Ce--La Ce--La Dop NW Pm
Sm Eu Gd Li.sub.2O Pm/ Sm/ Eu/ Gd/ Li.sub.2O Li.sub.2O Li.sub.2O
Li.sub.2O Na.sub.2O Pm/ Sm/ Eu/ Gd/ Na.sub.2O Na.sub.2O Na.sub.2O
Na.sub.2O K.sub.2O Pm/ Sm/ Eu/ Gd/ K.sub.2O K.sub.2O K.sub.2O
K.sub.2O Rb.sub.2O Pm/ Sm/ Eu/ Gd/ Rb.sub.2O Rb.sub.2O Rb.sub.2O
Rb.sub.2O Cs.sub.2O Pm/ Sm/ Eu/ Gd/ Cs.sub.2O Cs.sub.2O Cs.sub.2O
Cs.sub.2O BeO Pm/ Sm/ Eu/ Gd/ BeO BeO BeO BeO MgO Pm/ Sm/ Eu/ Gd/
MgO MgO MgO MgO CaO Pm/ Sm/ Eu/ Gd/ CaO CaO CaO CaO SrO Pm/ Sm/ Eu/
Gd/ SrO SrO SrO SrO BaO Pm/ Sm/ Eu/ Gd/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Y.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3
CeO.sub.2 Pm/ Sm/ Eu/ Gd/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2
Ce.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Eu.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2 Pm/ Sm/ Eu/ Gd/ TbO.sub.2
TbO.sub.2 TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Pm/ Sm/ Eu/ Gd/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Pm/ Sm/ Eu/ Gd/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Pm/ Sm/ Eu/ Gd/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Pm/ Sm/ Eu/ Gd/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Pm/ Sm/ Eu/ Gd/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Pm/ Sm/ Eu/ Gd/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Pm/ Sm/ Eu/ Gd/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Pm/ Sm/ Eu/ Gd/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Pm/ Sm/ Eu/ Gd/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Pm/ Sm/ Eu/ Gd/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Pm/ Sm/ Eu/ Gd/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Pm/ Sm/ Eu/ Gd/ VO VO VO VO
V.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Pm/ Sm/ Eu/ Gd/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Pm/ Sm/ Eu/ Gd/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Pm/ Sm/ Eu/ Gd/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Pm/ Sm/ Eu/ Gd/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Pm/ Sm/ Eu/ Gd/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Pm/ Sm/ Eu/ Gd/ NbO NbO NbO NbO
NbO.sub.2 Pm/ Sm/ Eu/ Gd/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Pm/ Sm/ Eu/ Gd/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Pm/ Sm/ Eu/ Gd/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Pm/ Sm/ Eu/ Gd/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Pm/ Sm/ Eu/ Gd/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Pm/ Sm/ Eu/ Gd/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Pm/ Sm/ Eu/ Gd/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Pm/ Sm/ Eu/ Gd/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Pm/ Sm/ Eu/ Gd/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Pm/ Sm/ Eu/ Gd/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Pm/ Sm/ Eu/ Gd/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Pm/ Sm/ Eu/ Gd/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Pm/ Sm/ Eu/ Gd/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Pm/ Sm/ Eu/ Gd/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Pm/ Sm/ Eu/ Gd/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Pm/ Sm/ Eu/ Gd/ MnO MnO MnO MnO
Mn/Mg/O Pm/ Sm/ Eu/ Gd/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Pm/ Sm/ Eu/ Gd/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Pm/ Sm/ Eu/ Gd/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Pm/ Sm/ Eu/ Gd/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Pm/ Sm/ Eu/ Gd/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Pm/ Sm/ Eu/ Gd/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Pm/ Sm/ Eu/ Gd/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Pm/ Sm/ Eu/ Gd/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Pm/ Sm/ Eu/ Gd/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Pm/ Sm/ Eu/ Gd/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Pm/ Sm/ Eu/ Gd/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Pm/ Sm/ Eu/ Gd/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8 Pm/ Sm/ Eu/ Gd/
(Li,Mg).sub.6MnO8 (Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 Mn.sub.2O.sub.4 Pm/ Sm/ Eu/ Gd/
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Na.sub.4P.sub.2O.sub.7 Pm/ Sm/ Eu/ Gd/ Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Pm/ Sm/ Eu/ Gd/
Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mn.sub.3O.sub.4/WO.sub.4 Pm/ Sm/ Eu/ Gd/ Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4 Pm/ Sm/ Eu/ Gd/
Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Zr.sub.2Mo.sub.2O.sub.8 Pm/ Sm/ Eu/ Gd/ Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Pm/ Sm/ Eu/ Gd/ MgO
NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/ MgO MgO
MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Pm/ Sm/ Eu/ Gd/
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Pm/ Sm/ Eu/ Gd/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Pm/ Sm/ Eu/ Gd/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Pm/ Sm/ Eu/ Gd/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Pm/ Sm/ Eu/ Gd/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Pm/ Sm/ Eu/ Gd/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Pm/ Sm/ Eu/ Gd/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Pm/ Sm/ Eu/ Gd/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Pm/
Sm/ Eu/ Gd/ Y--La Y--La Y--La Y--La Zr--La Pm/ Sm/ Eu/ Gd/ Zr--La
Zr--La Zr--La Zr--La Pr--La Pm/ Sm/ Eu/ Gd/ Pr--La Pr--La Pr--La
Pr--La Ce--La Pm/ Sm/ Eu/ Gd/ Ce--La Ce--La Ce--La Ce--La
TABLE-US-00004 TABLE 4 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Tb Dy Ho Er Li.sub.2O Tb/ Dy/ Ho/ Er/ Li.sub.2O
Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O Tb/ Dy/ Ho/ Er/ Na.sub.2O
Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O Tb/ Dy/ Ho/ Er/ K.sub.2O
K.sub.2O K.sub.2O K.sub.2O Rb.sub.2O Tb/ Dy/ Ho/ Er/ Rb.sub.2O
Rb.sub.2O Rb.sub.2O Rb.sub.2O Cs.sub.2O Tb/ Dy/ Ho/ Er/ Cs.sub.2O
Cs.sub.2O Cs.sub.2O Cs.sub.2O BeO Tb/ Dy/ Ho/ Er/ BeO BeO BeO BeO
MgO Tb/ Dy/ Ho/ Er/ MgO MgO MgO MgO CaO Tb/ Dy/ Ho/ Er/ CaO CaO CaO
CaO SrO Tb/ Dy/ Ho/ Er/ SrO SrO SrO SrO BaO Tb/ Dy/ Ho/ Er/ BaO BaO
BaO BaO Sc.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Tb/
Dy/ Ho/ Er/ Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 La.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Tb/ Dy/
Ho/ Er/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Tb/
Dy/ Ho/ Er/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Tb/
Dy/ Ho/ Er/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Tb/
Dy/ Ho/ Er/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb/
Dy/ Ho/ Er/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 TbO.sub.2 Tb/ Dy/ Ho/ Er/ TbO.sub.2 TbO.sub.2
TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Tb/ Dy/ Ho/ Er/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Tb/ Dy/ Ho/ Er/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Tb/ Dy/ Ho/ Er/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Tb/ Dy/ Ho/ Er/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Tb/ Dy/ Ho/ Er/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Tb/ Dy/ Ho/ Er/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Tb/ Dy/ Ho/ Er/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Tb/ Dy/ Ho/ Er/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Tb/ Dy/ Ho/ Er/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Tb/ Dy/ Ho/ Er/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Tb/ Dy/ Ho/ Er/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Tb/ Dy/ Ho/ Er/ VO VO VO VO
V.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Tb/ Dy/ Ho/ Er/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Tb/ Dy/ Ho/ Er/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Tb/ Dy/ Ho/ Er/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Tb/ Dy/ Ho/ Er/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Tb/ Dy/ Ho/ Er/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Tb/ Dy/ Ho/ Er/ NbO NbO NbO NbO
NbO.sub.2 Tb/ Dy/ Ho/ Er/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Tb/ Dy/ Ho/ Er/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Tb/ Dy/ Ho/ Er/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Tb/ Dy/ Ho/ Er/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Tb/ Dy/ Ho/ Er/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Tb/ Dy/ Ho/ Er/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Tb/ Dy/ Ho/ Er/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Tb/ Dy/ Ho/ Er/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Tb/ Dy/ Ho/ Er/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Tb/ Dy/ Ho/ Er/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Tb/ Dy/ Ho/ Er/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Tb/ Dy/ Ho/ Er/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Tb/ Dy/ Ho/ Er/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Tb/ Dy/ Ho/ Er/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Tb/ Dy/ Ho/ Er/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Tb/ Dy/ Ho/ Er/ MnO MnO MnO MnO
Mn/Mg/O Tb/ Dy/ Ho/ Er/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Tb/ Dy/ Ho/ Er/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Tb/ Dy/ Ho/ Er/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Tb/ Dy/ Ho/ Er/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Tb/ Dy/ Ho/ Er/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Tb/ Dy/ Ho/ Er/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Tb/ Dy/ Ho/ Er/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Tb/ Dy/ Ho/ Er/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Tb/ Dy/ Ho/ Er/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Tb/ Dy/ Ho/ Er/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Tb/ Dy/ Ho/ Er/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Tb/ Dy/ Ho/ Er/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Tb/ Dy/ Ho/ Er/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6MnO.sub.8 Tb/ Dy/ Ho/ Er/ (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Tb/ Dy/ Ho/ Er/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Tb/
Dy/ Ho/ Er/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Tb/ Dy/ Ho/ Er/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Tb/ Dy/ Ho/ Er/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Tb/ Dy/ Ho/ Er/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Tb/
Dy/ Ho/ Er/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Tb/ Dy/
Ho/ Er/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Tb/ Dy/ Ho/ Er/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Tb/ Dy/ Ho/ Er/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Tb/ Dy/ Ho/ Er/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Tb/ Dy/ Ho/ Er/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Tb/ Dy/ Ho/ Er/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Tb/ Dy/ Ho/ Er/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Tb/ Dy/ Ho/ Er/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Tb/
Dy/ Ho/ Er/ Y--La Y--La Y--La Y--La Zr--La Tb/ Dy/ Ho/ Er/ Zr--La
Zr--La Zr--La Zr--La Pr--La Tb/ Dy/ Ho/ Er/ Pr--La Pr--La Pr--La
Pr--La Ce--La Tb/ Dy/ Ho/ Er/ Ce--La Ce--La Ce--La Ce--La Dop NW Tm
Yb Lu In Li.sub.2O Tm/ Yb/ Lu/ In/ Li.sub.2O Li.sub.2O Li.sub.2O
Li.sub.2O Na.sub.2O Tm/ Yb/ Lu/ In/ Na.sub.2O Na.sub.2O Na.sub.2O
Na.sub.2O K.sub.2O Tm/ Yb/ Lu/ In/ K.sub.2O K.sub.2O K.sub.2O
K.sub.2O Rb.sub.2O Tm/ Yb/ Lu/ In/ Rb.sub.2O Rb.sub.2O Rb.sub.2O
Rb.sub.2O Cs.sub.2O Tm/ Yb/ Lu/ In/ Cs.sub.2O Cs.sub.2O Cs.sub.2O
Cs.sub.2O BeO Tm/ Yb/ Lu/ In/ BeO BeO BeO BeO MgO Tm/ Yb/ Lu/ In/
MgO MgO MgO MgO CaO Tm/ Yb/ Lu/ In/ CaO CaO CaO CaO SrO Tm/ Yb/ Lu/
In/ SrO SrO SrO SrO BaO Tm/ Yb/ Lu/ In/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Y.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3
CeO.sub.2 Tm/ Yb/ Lu/ In/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2
Ce.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Eu.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2 Tm/ Yb/ Lu/ In/ TbO.sub.2
TbO.sub.2 TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Tm/ Yb/ Lu/ In/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Tm/ Yb/ Lu/ In/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Tm/ Yb/ Lu/ In/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Tm/ Yb/ Lu/ In/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Tm/ Yb/ Lu/ In/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Tm/ Yb/ Lu/ In/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Tm/ Yb/ Lu/ In/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Tm/ Yb/ Lu/ In/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Tm/ Yb/ Lu/ In/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Tm/ Yb/ Lu/ In/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Tm/ Yb/ Lu/ In/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Tm/ Yb/ Lu/ In/ VO VO VO VO
V.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Tm/ Yb/ Lu/ In/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Tm/ Yb/ Lu/ In/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Tm/ Yb/ Lu/ In/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Tm/ Yb/ Lu/ In/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Tm/ Yb/ Lu/ In/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Tm/ Yb/ Lu/ In/ NbO NbO NbO NbO
NbO.sub.2 Tm/ Yb/ Lu/ In/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Tm/ Yb/ Lu/ In/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Tm/ Yb/ Lu/ In/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Tm/ Yb/ Lu/ In/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Tm/ Yb/ Lu/ In/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Tm/ Yb/ Lu/ In/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Tm/ Yb/ Lu/ In/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Tm/ Yb/ Lu/ In/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Tm/ Yb/ Lu/ In/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Tm/ Yb/ Lu/ In/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Tm/ Yb/ Lu/ In/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Tm/ Yb/ Lu/ In/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Tm/ Yb/ Lu/ In/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Tm/ Yb/ Lu/ In/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Tm/ Yb/ Lu/ In/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Tm/ Yb/ Lu/ In/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Tm/ Yb/ Lu/ In/ MnO MnO MnO MnO
Mn/Mg/O Tm/ Yb/ Lu/ In/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Tm/ Yb/ Lu/ In/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Tm/ Yb/ Lu/ In/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Tm/ Yb/ Lu/ In/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Tm/ Yb/ Lu/ In/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Tm/ Yb/ Lu/ In/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Tm/ Yb/ Lu/ In/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Tm/ Yb/ Lu/ In/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Tm/ Yb/ Lu/ In/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Tm/ Yb/ Lu/ In/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Tm/ Yb/ Lu/ In/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Tm/ Yb/ Lu/ In/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Tm/ Yb/ Lu/ In/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6MnO.sub.8 Tm/ Yb/ Lu/ In/ (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Tm/ Yb/ Lu/ In/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Tm/
Yb/ Lu/ In/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Tm/ Yb/ Lu/ In/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Tm/ Yb/ Lu/ In/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Tm/ Yb/ Lu/ In/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Tm/
Yb/ Lu/ In/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Tm/ Yb/
Lu/ In/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Tm/ Yb/ Lu/ In/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Tm/ Yb/ Lu/ In/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Tm/ Yb/ Lu/ In/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Tm/ Yb/ Lu/ In/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Tm/ Yb/ Lu/ In/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Tm/ Yb/ Lu/ In/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Tm/ Yb/ Lu/ In/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Tm/
Yb/ Lu/ In/ Y--La Y--La Y--La Y--La Zr--La Tm/ Yb/ Lu/ In/ Zr--La
Zr--La Zr--La Zr--La Pr--La Tm/ Yb/ Lu/ In/ Pr--La Pr--La Pr--La
Pr--La Ce--La Tm/ Yb/ Lu/ In/ Ce--La Ce--La Ce--La Ce--La
TABLE-US-00005 TABLE 5 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Y Sc Al Cu Li.sub.2O Y/ Sc/ Al/ Cu/ Li.sub.2O
Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O Y/ Sc/ Al/ Cu/ Na.sub.2O
Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O Y/ Sc/ Al/ Cu/ K.sub.2O
K.sub.2O K.sub.2O K.sub.2O Rb.sub.2O Y/ Sc/ Al/ Cu/ Rb.sub.2O
Rb.sub.2O Rb.sub.2O Rb.sub.2O Cs.sub.2O Y/ Sc/ Al/ Cu/ Cs.sub.2O
Cs.sub.2O Cs.sub.2O Cs.sub.2O BeO Y/ Sc/ Al/ Cu/ BeO BeO BeO BeO
MgO Y/ Sc/ Al/ Cu/ MgO MgO MgO MgO CaO Y/ Sc/ Al/ Cu/ CaO CaO CaO
CaO SrO Y/ Sc/ Al/ Cu/ SrO SrO SrO SrO BaO Y/ Sc/ Al/ Cu/ BaO BaO
BaO BaO Sc.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Y/
Sc/ Al/ Cu/ Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 La.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Y/ Sc/
Al/ Cu/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Y/
Sc/ Al/ Cu/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Y/
Sc/ Al/ Cu/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Y/
Sc/ Al/ Cu/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Y/
Sc/ Al/ Cu/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 TbO.sub.2 Y/ Sc/ Al/ Cu/ TbO.sub.2 TbO.sub.2
TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Y/ Sc/ Al/ Cu/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Y/ Sc/ Al/ Cu/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Y/ Sc/ Al/ Cu/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Y/ Sc/ Al/ Cu/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Y/ Sc/ Al/ Cu/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Y/ Sc/ Al/ Cu/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Y/ Sc/ Al/ Cu/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Y/ Sc/ Al/ Cu/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Y/ Sc/ Al/ Cu/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Y/ Sc/ Al/ Cu/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Y/ Sc/ Al/ Cu/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Y/ Sc/ Al/ Cu/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Y/ Sc/ Al/ Cu/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Y/ Sc/ Al/ Cu/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Y/ Sc/ Al/ Cu/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Y/ Sc/ Al/ Cu/ VO VO VO VO
V.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Y/ Sc/ Al/ Cu/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Y/ Sc/ Al/ Cu/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Y/ Sc/ Al/ Cu/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Y/ Sc/ Al/ Cu/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Y/ Sc/ Al/ Cu/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Y/ Sc/ Al/ Cu/ NbO NbO NbO NbO
NbO.sub.2 Y/ Sc/ Al/ Cu/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Y/ Sc/ Al/ Cu/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Y/ Sc/ Al/ Cu/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Y/ Sc/ Al/ Cu/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Y/ Sc/ Al/ Cu/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Y/ Sc/ Al/ Cu/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Y/ Sc/ Al/ Cu/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Y/ Sc/ Al/ Cu/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Y/ Sc/ Al/ Cu/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Y/ Sc/ Al/ Cu/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Y/ Sc/ Al/ Cu/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Y/ Sc/ Al/ Cu/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Y/ Sc/ Al/ Cu/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Y/ Sc/ Al/ Cu/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Y/ Sc/ Al/ Cu/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Y/ Sc/ Al/ Cu/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Y/ Sc/ Al/ Cu/ MnO MnO MnO MnO
Mn/Mg/O Y/ Sc/ Al/ Cu/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Y/ Sc/ Al/ Cu/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Y/ Sc/ Al/ Cu/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Y/ Sc/ Al/ Cu/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Y/ Sc/ Al/ Cu/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Y/ Sc/ Al/ Cu/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Y/ Sc/ Al/ Cu/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Y/ Sc/ Al/ Cu/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Y/ Sc/ Al/ Cu/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Y/ Sc/ Al/ Cu/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Y/ Sc/ Al/ Cu/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Y/ Sc/ Al/ Cu/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Y/ Sc/ Al/ Cu/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6MnO.sub.8 Y/ Sc/ Al/ Cu/ (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Y/ Sc/ Al/ Cu/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Y/
Sc/ Al/ Cu/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Y/ Sc/ Al/ Cu/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Y/ Sc/ Al/ Cu/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Y/ Sc/ Al/ Cu/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Y/
Sc/ Al/ Cu/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Y/ Sc/
Al/ Cu/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Y/ Sc/ Al/ Cu/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Y/ Sc/ Al/ Cu/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Y/ Sc/ Al/ Cu/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Y/ Sc/ Al/ Cu/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Y/ Sc/ Al/ Cu/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Y/ Sc/ Al/ Cu/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Y/ Sc/ Al/ Cu/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Y/
Sc/ Al/ Cu/ Y--La Y--La Y--La Y--La Zr--La Y/ Sc/ Al/ Cu/ Zr--La
Zr--La Zr--La Zr--La Pr--La Y/ Sc/ Al/ Cu/ Pr--La Pr--La Pr--La
Pr--La Ce--La Y/ Sc/ Al/ Cu/ Ce--La Ce--La Ce--La Ce--La Dop NW Ga
Hf Fe Cr Li.sub.2O Ga/ Hf/ Fe/ Cr/ Li.sub.2O Li.sub.2O Li.sub.2O
Li.sub.2O Na.sub.2O Ga/ Hf/ Fe/ Cr/ Na.sub.2O Na.sub.2O Na.sub.2O
Na.sub.2O K.sub.2O Ga/ Hf/ Fe/ Cr/ K.sub.2O K.sub.2O K.sub.2O
K.sub.2O Rb.sub.2O Ga/ Hf/ Fe/ Cr/ Rb.sub.2O Rb.sub.2O Rb.sub.2O
Rb.sub.2O Cs.sub.2O Ga/ Hf/ Fe/ Cr/ Cs.sub.2O Cs.sub.2O Cs.sub.2O
Cs.sub.2O BeO Ga/ Hf/ Fe/ Cr/ BeO BeO BeO BeO MgO Ga/ Hf/ Fe/ Cr/
MgO MgO MgO MgO CaO Ga/ Hf/ Fe/ Cr/ CaO CaO CaO CaO SrO Ga/ Hf/ Fe/
Cr/ SrO SrO SrO SrO BaO Ga/ Hf/ Fe/ Cr/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Y.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3
CeO.sub.2 Ga/ Hf/ Fe/ Cr/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2
Ce.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Eu.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2 Ga/ Hf/ Fe/ Cr/ TbO.sub.2
TbO.sub.2 TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Ga/ Hf/ Fe/ Cr/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Ga/ Hf/ Fe/ Cr/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Ga/ Hf/ Fe/ Cr/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Ga/ Hf/ Fe/ Cr/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Ga/ Hf/ Fe/ Cr/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Ga/ Hf/ Fe/ Cr/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Ga/ Hf/ Fe/ Cr/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Ga/ Hf/ Fe/ Cr/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Ga/ Hf/ Fe/ Cr/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Ga/ Hf/ Fe/ Cr/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Ga/ Hf/ Fe/ Cr/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Ga/ Hf/ Fe/ Cr/ VO VO VO VO
V.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Ga/ Hf/ Fe/ Cr/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Ga/ Hf/ Fe/ Cr/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Ga/ Hf/ Fe/ Cr/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Ga/ Hf/ Fe/ Cr/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Ga/ Hf/ Fe/ Cr/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Ga/ Hf/ Fe/ Cr/ NbO NbO NbO NbO
NbO.sub.2 Ga/ Hf/ Fe/ Cr/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Ga/ Hf/ Fe/ Cr/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Ga/ Hf/ Fe/ Cr/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Ga/ Hf/ Fe/ Cr/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Ga/ Hf/ Fe/ Cr/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Ga/ Hf/ Fe/ Cr/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Ga/ Hf/ Fe/ Cr/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Ga/ Hf/ Fe/ Cr/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Ga/ Hf/ Fe/ Cr/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Ga/ Hf/ Fe/ Cr/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Ga/ Hf/ Fe/ Cr/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Ga/ Hf/ Fe/ Cr/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Ga/ Hf/ Fe/ Cr/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Ga/ Hf/ Fe/ Cr/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Ga/ Hf/ Fe/ Cr/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Ga/ Hf/ Fe/ Cr/ MnO MnO MnO MnO
Mn/Mg/O Ga/ Hf/ Fe/ Cr/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Ga/ Hf/ Fe/ Cr/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Ga/ Hf/ Fe/ Cr/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Ga/ Hf/ Fe/ Cr/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Ga/ Hf/ Fe/ Cr/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Ga/ Hf/ Fe/ Cr/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Ga/ Hf/ Fe/ Cr/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Ga/ Hf/ Fe/ Cr/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Ga/ Hf/ Fe/ Cr/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Ga/ Hf/ Fe/ Cr/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Ga/ Hf/ Fe/ Cr/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Ga/ Hf/ Fe/ Cr/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Ga/ Hf/ Fe/ Cr/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6MnO.sub.8 Ga/ Hf/ Fe/ Cr/ (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 (Li,Mg).sub.6MnO.sub.8
(Li,Mg).sub.6MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Ga/ Hf/ Fe/ Cr/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Ga/
Hf/ Fe/ Cr/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Ga/ Hf/ Fe/ Cr/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Ga/ Hf/ Fe/ Cr/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Ga/ Hf/ Fe/ Cr/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Ga/
Hf/ Fe/ Cr/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Ga/ Hf/
Fe/ Cr/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Ga/ Hf/ Fe/ Cr/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Ga/ Hf/ Fe/ Cr/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Ga/ Hf/ Fe/ Cr/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Ga/ Hf/ Fe/ Cr/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Ga/ Hf/ Fe/ Cr/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Ga/ Hf/ Fe/ Cr/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Ga/ Hf/ Fe/ Cr/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Ga/
Hf/ Fe/ Cr/ Y--La Y--La Y--La Y--La Zr--La Ga/ Hf/ Fe/ Cr/ Zr--La
Zr--La Zr--La Zr--La Pr--La Ga/ Hf/ Fe/ Cr/ Pr--La Pr--La Pr--La
Pr--La Ce--La Ga/ Hf/ Fe/ Cr/ Ce--La Ce--La Ce--La Ce--La
TABLE-US-00006 TABLE 6 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Ru Zr Ta Rh Li.sub.2O Ru/ Zr/ Ta/ Rh/ Li.sub.2O
Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O Ru/ Zr/ Ta/ Rh/ Na.sub.2O
Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O Ru/ Zr/ Ta/ Rh/ K.sub.2O
K.sub.2O K.sub.2O K.sub.2O Rb.sub.2O Ru/ Zr/ Ta/ Rh/ Rb.sub.2O
Rb.sub.2O Rb.sub.2O Rb.sub.2O Cs.sub.2O Ru/ Zr/ Ta/ Rh/ Cs.sub.2O
Cs.sub.2O Cs.sub.2O Cs.sub.2O BeO Ru/ Zr/ Ta/ Rh/ BeO BeO BeO BeO
MgO Ru/ Zr/ Ta/ Rh/ MgO MgO MgO MgO CaO Ru/ Zr/ Ta/ Rh/ CaO CaO CaO
CaO SrO Ru/ Zr/ Ta/ Rh/ SrO SrO SrO SrO BaO Ru/ Zr/ Ta/ Rh/ BaO BaO
BaO BaO Sc.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Ru/
Zr/ Ta/ Rh/ Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 La.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Ru/ Zr/
Ta/ Rh/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Ru/
Zr/ Ta/ Rh/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Ru/
Zr/ Ta/ Rh/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Ru/
Zr/ Ta/ Rh/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Ru/
Zr/ Ta/ Rh/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 TbO.sub.2 Ru/ Zr/ Ta/ Rh/ TbO.sub.2 TbO.sub.2
TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Ru/ Zr/ Ta/ Rh/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Ru/ Zr/ Ta/ Rh/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Ru/ Zr/ Ta/ Rh/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Ru/ Zr/ Ta/ Rh/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Ru/ Zr/ Ta/ Rh/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Ru/ Zr/ Ta/ Rh/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Ru/ Zr/ Ta/ Rh/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Ru/ Zr/ Ta/ Rh/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Ru/ Zr/ Ta/ Rh/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Ru/ Zr/ Ta/ Rh/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Ru/ Zr/ Ta/ Rh/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Ru/ Zr/ Ta/ Rh/ VO VO VO VO
V.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Ru/ Zr/ Ta/ Rh/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Ru/ Zr/ Ta/ Rh/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Ru/ Zr/ Ta/ Rh/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Ru/ Zr/ Ta/ Rh/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Ru/ Zr/ Ta/ Rh/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Ru/ Zr/ Ta/ Rh/ NbO NbO NbO NbO
NbO.sub.2 Ru/ Zr/ Ta/ Rh/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Ru/ Zr/ Ta/ Rh/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Ru/ Zr/ Ta/ Rh/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Ru/ Zr/ Ta/ Rh/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Ru/ Zr/ Ta/ Rh/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Ru/ Zr/ Ta/ Rh/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Ru/ Zr/ Ta/ Rh/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Ru/ Zr/ Ta/ Rh/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Ru/ Zr/ Ta/ Rh/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Ru/ Zr/ Ta/ Rh/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Ru/ Zr/ Ta/ Rh/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Ru/ Zr/ Ta/ Rh/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Ru/ Zr/ Ta/ Rh/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Ru/ Zr/ Ta/ Rh/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Ru/ Zr/ Ta/ Rh/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Ru/ Zr/ Ta/ Rh/ MnO MnO MnO MnO
Mn/Mg/O Ru/ Zr/ Ta/ Rh/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Ru/ Zr/ Ta/ Rh/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Ru/ Zr/ Ta/ Rh/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Ru/ Zr/ Ta/ Rh/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Ru/ Zr/ Ta/ Rh/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Ru/ Zr/ Ta/ Rh/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Ru/ Zr/ Ta/ Rh/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Ru/ Zr/ Ta/ Rh/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Ru/ Zr/ Ta/ Rh/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Ru/ Zr/ Ta/ Rh/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Ru/ Zr/ Ta/ Rh/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Ru/ Zr/ Ta/ Rh/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Ru/ Zr/ Ta/ Rh/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6--MnO.sub.8 Ru/ Zr/ Ta/ Rh/ (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Ru/ Zr/ Ta/ Rh/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Ru/
Zr/ Ta/ Rh/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Ru/ Zr/ Ta/ Rh/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Ru/ Zr/ Ta/ Rh/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Ru/ Zr/ Ta/ Rh/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Ru/
Zr/ Ta/ Rh/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Ru/ Zr/
Ta/ Rh/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Ru/ Zr/ Ta/ Rh/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Ru/ Zr/ Ta/ Rh/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Ru/ Zr/ Ta/ Rh/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Ru/ Zr/ Ta/ Rh/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Ru/ Zr/ Ta/ Rh/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Ru/ Zr/ Ta/ Rh/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Ru/ Zr/ Ta/ Rh/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Ru/
Zr/ Ta/ Rh/ Y--La Y--La Y--La Y--La Zr--La Ru/ Zr/ Ta/ Rh/ Zr--La
Zr--La Zr--La Zr--La Pr--La Ru/ Zr/ Ta/ Rh/ Pr--La Pr--La Pr--La
Pr--La Ce--La Ru/ Zr/ Ta/ Rh/ Ce--La Ce--La Ce--La Ce--La Dop NW Au
Mo Ni Li.sub.2O Au/ Mo/ Ni/ Li.sub.2O Li.sub.2O Li.sub.2O Na.sub.2O
Au/ Mo/ Ni/ Na.sub.2O Na.sub.2O Na.sub.2O K.sub.2O Au/ Mo/ Ni/
K.sub.2O K.sub.2O K.sub.2O Rb.sub.2O Au/ Mo/ Ni/ Rb.sub.2O
Rb.sub.2O Rb.sub.2O Cs.sub.2O Au/ Mo/ Ni/ Cs.sub.2O Cs.sub.2O
Cs.sub.2O BeO Au/ Mo/ Ni/ BeO BeO BeO MgO Au/ Mo/ Ni/ MgO MgO MgO
CaO Au/ Mo/ Ni/ CaO CaO CaO SrO Au/ Mo/ Ni/ SrO SrO SrO BaO Au/ Mo/
Ni/ BaO BaO BaO Sc.sub.2O.sub.3 Au/ Mo/ Ni/ Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Y.sub.2O.sub.3 Au/ Mo/ Ni/ Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 La.sub.2O.sub.3 Au/ Mo/ Ni/ La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Au/ Mo/ Ni/ CeO.sub.2
CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Au/ Mo/ Ni/ Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Au/ Mo/ Ni/
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Au/
Mo/ Ni/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Sm.sub.2O.sub.3 Au/ Mo/ Ni/ Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Au/ Mo/ Ni/ Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Au/ Mo/ Ni/
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Au/
Mo/ Ni/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2
Au/ Mo/ Ni/ TbO.sub.2 TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Au/ Mo/
Ni/ Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Au/ Mo/ Ni/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Au/ Mo/ Ni/ Ho.sub.2O.sub.3
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Er.sub.2O.sub.3 Au/ Mo/ Ni/
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Au/
Mo/ Ni/ Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Au/ Mo/ Ni/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Au/ Mo/ Ni/ Lu.sub.2O.sub.3
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Ac.sub.2O.sub.3 Au/ Mo/ Ni/
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Au/
Mo/ Ni/ Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 ThO.sub.2
Au/ Mo/ Ni/ ThO.sub.2 ThO.sub.2 ThO.sub.2 Pa.sub.2O.sub.3 Au/ Mo/
Ni/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Au/
Mo/ Ni/ PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Au/ Mo/ Ni/
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Au/ Mo/ Ni/ TiO TiO TiO
Ti.sub.2O.sub.3 Au/ Mo/ Ni/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.3O Au/ Mo/ Ni/ Ti.sub.3O Ti.sub.3O Ti.sub.3O
Ti.sub.2O Au/ Mo/ Ni/ Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5
Au/ Mo/ Ni/ Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Au/ Mo/ Ni/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 ZrO.sub.2 Au/ Mo/ Ni/ ZrO.sub.2 ZrO.sub.2 ZrO.sub.2
HfO.sub.2 Au/ Mo/ Ni/ HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Au/ Mo/ Ni/
VO VO VO V.sub.2O.sub.3 Au/ Mo/ Ni/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 VO.sub.2 Au/ Mo/ Ni/ VO.sub.2 VO.sub.2 VO.sub.2
V.sub.2O.sub.5 Au/ Mo/ Ni/ V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.2O.sub.5 V.sub.3O.sub.7 Au/ Mo/ Ni/ V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Au/ Mo/ Ni/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.6O.sub.13 Au/
Mo/ Ni/ V.sub.6O.sub.13 V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Au/ Mo/
Ni/ NbO NbO NbO NbO.sub.2 Au/ Mo/ Ni/ NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Au/ Mo/ Ni/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Au/ Mo/ Ni/ Nb.sub.8O.sub.19
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.16O.sub.38 Au/ Mo/ Ni/
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Au/ Mo/ Ni/ Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.47O.sub.116 Au/ Mo/ Ni/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Ta.sub.2O.sub.5 Au/ Mo/ Ni/
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Au/ Mo/ Ni/ CrO
CrO CrO Cr.sub.2O.sub.3 Au/ Mo/ Ni/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 CrO.sub.2 Au/ Mo/ Ni/ CrO.sub.2 CrO.sub.2 CrO.sub.2
CrO.sub.3 Au/ Mo/ Ni/ CrO.sub.3 CrO.sub.3 CrO.sub.3
Cr.sub.8O.sub.21 Au/ Mo/ Ni/ Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
Cr.sub.8O.sub.21 MoO.sub.2 Au/ Mo/ Ni/ MoO.sub.2 MoO.sub.2
MoO.sub.2 MoO.sub.3 Au/ Mo/ Ni/ MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Au/ Mo/ Ni/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 WoO.sub.2 Au/ Mo/ Ni/ WoO.sub.2 WoO.sub.2 WoO.sub.2
WoO.sub.3 Au/ Mo/ Ni/ WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Au/ Mo/ Ni/
MnO MnO MnO Mn/Mg/O Au/ Mo/ Ni/ Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Au/ Mo/ Ni/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Au/ Mo/ Ni/ Mn.sub.2O.sub.3
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 MnO.sub.2 Au/ Mo/ Ni/ MnO.sub.2
MnO.sub.2 MnO.sub.2 Mn.sub.2O.sub.7 Au/ Mo/ Ni/ Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Au/ Mo/ Ni/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.3 Au/ Mo/ Ni/ ReO.sub.3 ReO.sub.3
ReO.sub.3 Re.sub.2O.sub.7 Au/ Mo/ Ni/ Re.sub.2O.sub.7
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Au/ Mo/ Ni/ Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Au/ Mo/ Ni/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Au/
Mo/ Ni/ NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Au/ Mo/
Ni/ Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mn.sub.2O.sub.4 Au/ Mo/ Ni/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 (Li,Mg).sub.6--MnO.sub.8 Au/ Mo/ Ni/
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8
Na.sub.4P.sub.2O.sub.7 Au/ Mo/ Ni/ Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Au/
Mo/ Ni/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mn.sub.3O.sub.4/WO.sub.4 Au/ Mo/ Ni/ Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Au/ Mo/ Ni/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Zr.sub.2Mo.sub.2O.sub.8 Au/ Mo/ Ni/ Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Au/
Mo/ Ni/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/ MgO MgO
MgO Na.sub.10Mn--W.sub.5O.sub.17 Au/ Mo/ Ni/
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 La.sub.3NdO.sub.6 Au/ Mo/ Ni/
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Au/ Mo/ Ni/ LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6 Au/ Mo/ Ni/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6 Au/ Mo/ Ni/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6 Au/ Mo/ Ni/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6 Au/ Mo/ Ni/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Au/ Mo/ Ni/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Au/ Mo/ Ni/ Y--La Y--La Y--La
Zr--La Au/ Mo/ Ni/ Zr--La Zr--La Zr--La Pr--La Au/ Mo/ Ni/ Pr--La
Pr--La Pr--La Ce--La Au/ Mo/ Ni/ Ce--La Ce--La Ce--La
TABLE-US-00007 TABLE 7 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Co Sb W V Li.sub.2O Co/ Sb/ W/ V/ Li.sub.2O Li.sub.2O
Li.sub.2O Li.sub.2O Na.sub.2O Co/ Sb/ W/ V/ Na.sub.2O Na.sub.2O
Na.sub.2O Na.sub.2O K.sub.2O Co/ Sb/ W/ V/ K.sub.2O K.sub.2O
K.sub.2O K.sub.2O Rb.sub.2O Co/ Sb/ W/ V/ Rb.sub.2O Rb.sub.2O
Rb.sub.2O Rb.sub.2O Cs.sub.2O Co/ Sb/ W/ V/ Cs.sub.2O Cs.sub.2O
Cs.sub.2O Cs.sub.2O BeO Co/ Sb/ W/ V/ BeO BeO BeO BeO MgO Co/ Sb/
W/ V/ MgO MgO MgO MgO CaO Co/ Sb/ W/ V/ CaO CaO CaO CaO SrO Co/ Sb/
W/ V/ SrO SrO SrO SrO BaO Co/ Sb/ W/ V/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Co/ Sb/ W/ V/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Co/ Sb/ W/ V/
Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3 Y.sub.2O.sub.3
La.sub.2O.sub.3 Co/ Sb/ W/ V/ La.sub.2O.sub.3 La.sub.2O.sub.3
La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Co/ Sb/ W/ V/ CeO.sub.2
CeO.sub.2 CeO.sub.2 CeO.sub.2 Ce.sub.2O.sub.3 Co/ Sb/ W/ V/
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Pr.sub.2O.sub.3 Co/ Sb/ W/ V/ Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Nd.sub.2O.sub.3 Co/ Sb/ W/ V/
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Sm.sub.2O.sub.3 Co/ Sb/ W/ V/ Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Eu.sub.2O.sub.3 Co/ Sb/ W/ V/
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Gd.sub.2O.sub.3 Co/ Sb/ W/ V/ Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Tb.sub.2O.sub.3 Co/ Sb/ W/ V/
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
TbO.sub.2 Co/ Sb/ W/ V/ TbO.sub.2 TbO.sub.2 TbO.sub.2 TbO.sub.2
Tb.sub.6O.sub.11 Co/ Sb/ W/ V/ Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Dy.sub.2O.sub.3 Co/ Sb/ W/ V/
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Ho.sub.2O.sub.3 Co/ Sb/ W/ V/ Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Er.sub.2O.sub.3 Co/ Sb/ W/ V/
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Er.sub.2O.sub.3 Er.sub.2O.sub.3
Tm.sub.2O.sub.3 Co/ Sb/ W/ V/ Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Yb.sub.2O.sub.3 Co/ Sb/ W/ V/
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Lu.sub.2O.sub.3 Co/ Sb/ W/ V/ Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Ac.sub.2O.sub.3 Co/ Sb/ W/ V/
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Th.sub.2O.sub.3 Co/ Sb/ W/ V/ Th.sub.2O.sub.3 Th.sub.2O.sub.3
Th.sub.2O.sub.3 Th.sub.2O.sub.3 ThO.sub.2 Co/ Sb/ W/ V/ ThO.sub.2
ThO.sub.2 ThO.sub.2 ThO.sub.2 Pa.sub.2O.sub.3 Co/ Sb/ W/ V/
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
PaO.sub.2 Co/ Sb/ W/ V/ PaO.sub.2 PaO.sub.2 PaO.sub.2 PaO.sub.2
TiO.sub.2 Co/ Sb/ W/ V/ TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO
Co/ Sb/ W/ V/ TiO TiO TiO TiO Ti.sub.2O.sub.3 Co/ Sb/ W/ V/
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.3O Co/ Sb/ W/ V/ Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.3O
Ti.sub.2O Co/ Sb/ W/ V/ Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.2O
Ti.sub.3O.sub.5 Co/ Sb/ W/ V/ Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.4O.sub.7 Co/ Sb/ W/ V/
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
ZrO.sub.2 Co/ Sb/ W/ V/ ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2
HfO.sub.2 Co/ Sb/ W/ V/ HfO.sub.2 HfO.sub.2 HfO.sub.2 HfO.sub.2 VO
Co/ Sb/ W/ V/ VO VO VO VO V.sub.2O.sub.3 Co/ Sb/ W/ V/
V.sub.2O.sub.3 V.sub.2O.sub.3 V.sub.2O.sub.3 V.sub.2O.sub.3
VO.sub.2 Co/ Sb/ W/ V/ VO.sub.2 VO.sub.2 VO.sub.2 VO.sub.2
V.sub.2O.sub.5 Co/ Sb/ W/ V/ V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.3O.sub.7 Co/ Sb/ W/ V/
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.4O.sub.9 Co/ Sb/ W/ V/ V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.6O.sub.13 Co/ Sb/ W/ V/
V.sub.6O.sub.13 V.sub.6O.sub.13 V.sub.6O.sub.13 V.sub.6O.sub.13 NbO
Co/ Sb/ W/ V/ NbO NbO NbO NbO NbO.sub.2 Co/ Sb/ W/ V/ NbO.sub.2
NbO.sub.2 NbO.sub.2 NbO.sub.2 Nb.sub.2O.sub.5 Co/ Sb/ W/ V/
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.8O.sub.19 Co/ Sb/ W/ V/ Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.16O.sub.38 Co/ Sb/ W/ V/
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.12O.sub.29 Co/ Sb/ W/ V/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Co/ Sb/ W/ V/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Co/ Sb/ W/ V/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Co/ Sb/ W/ V/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Co/ Sb/ W/ V/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Co/ Sb/ W/ V/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Co/ Sb/ W/ V/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Co/ Sb/ W/ V/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Co/ Sb/ W/ V/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Co/ Sb/ W/ V/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Co/ Sb/ W/ V/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Co/ Sb/ W/ V/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Co/ Sb/ W/ V/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Co/ Sb/ W/ V/ MnO MnO MnO MnO
Mn/Mg/O Co/ Sb/ W/ V/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Co/ Sb/ W/ V/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Co/ Sb/ W/ V/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Co/ Sb/ W/ V/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Co/ Sb/ W/ V/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Co/ Sb/ W/ V/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Co/ Sb/ W/ V/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Co/ Sb/ W/ V/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Co/ Sb/ W/ V/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Co/ Sb/ W/ V/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Co/ Sb/ W/ V/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Co/ Sb/ W/ V/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Co/ Sb/ W/ V/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6--MnO.sub.8 Co/ Sb/ W/ V/ (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Co/ Sb/ W/ V/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Co/
Sb/ W/ V/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Co/ Sb/ W/ V/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Co/ Sb/ W/ V/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Co/ Sb/ W/ V/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Co/
Sb/ W/ V/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Co/ Sb/
W/ V/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Co/ Sb/ W/ V/ La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 LaNd.sub.3O.sub.6 Co/ Sb/ W/ V/
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6 Co/ Sb/ W/ V/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Co/ Sb/ W/ V/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Co/ Sb/ W/ V/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Co/ Sb/ W/ V/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Co/ Sb/ W/ V/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Co/
Sb/ W/ V/ Y--La Y--La Y--La Y--La Zr--La Co/ Sb/ W/ V/ Zr--La
Zr--La Zr--La Zr--La Pr--La Co/ Sb/ W/ V/ Pr--La Pr--La Pr--La
Pr--La Ce--La Co/ Sb/ W/ V/ Ce--La Ce--La Ce--La Ce--La Dop NW Ag
Te Pd Ir Li.sub.2O Ag/ Te/ Pd/ Ir/ Li.sub.2O Li.sub.2O Li.sub.2O
Li.sub.2O Na.sub.2O Ag/ Te/ Pd/ Ir/ Na.sub.2O Na.sub.2O Na.sub.2O
Na.sub.2O K.sub.2O Ag/ Te/ Pd/ Ir/ K.sub.2O K.sub.2O K.sub.2O
K.sub.2O Rb.sub.2O Ag/ Te/ Pd/ Ir/ Rb.sub.2O Rb.sub.2O Rb.sub.2O
Rb.sub.2O Cs.sub.2O Ag/ Te/ Pd/ Ir/ Cs.sub.2O Cs.sub.2O Cs.sub.2O
Cs.sub.2O BeO Ag/ Te/ Pd/ Ir/ BeO BeO BeO BeO MgO Ag/ Te/ Pd/ Ir/
MgO MgO MgO MgO CaO Ag/ Te/ Pd/ Ir/ CaO CaO CaO CaO SrO Ag/ Te/ Pd/
Ir/ SrO SrO SrO SrO BaO Ag/ Te/ Pd/ Ir/ BaO BaO BaO BaO
Sc.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3
Y.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Y.sub.2O.sub.3 Y.sub.2O.sub.3
Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3 La.sub.2O.sub.3
CeO.sub.2 Ag/ Te/ Pd/ Ir/ CeO.sub.2 CeO.sub.2 CeO.sub.2 CeO.sub.2
Ce.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Ce.sub.2O.sub.3 Ce.sub.2O.sub.3 Pr.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Nd.sub.2O.sub.3 Nd.sub.2O.sub.3 Sm.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Eu.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Eu.sub.2O.sub.3 Eu.sub.2O.sub.3 Gd.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3
Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2 Ag/ Te/ Pd/ Ir/ TbO.sub.2
TbO.sub.2 TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Ag/ Te/ Pd/ Ir/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Tb.sub.6O.sub.11
Dy.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Dy.sub.2O.sub.3 Dy.sub.2O.sub.3
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Ho.sub.2O.sub.3
Er.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Er.sub.2O.sub.3 Er.sub.2O.sub.3
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Tm.sub.2O.sub.3
Yb.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Yb.sub.2O.sub.3 Yb.sub.2O.sub.3
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Lu.sub.2O.sub.3
Ac.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Ac.sub.2O.sub.3 Ac.sub.2O.sub.3
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3 Th.sub.2O.sub.3
ThO.sub.2 Ag/ Te/ Pd/ Ir/ ThO.sub.2 ThO.sub.2 ThO.sub.2 ThO.sub.2
Pa.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
Pa.sub.2O.sub.3 Pa.sub.2O.sub.3 PaO.sub.2 Ag/ Te/ Pd/ Ir/ PaO.sub.2
PaO.sub.2 PaO.sub.2 PaO.sub.2 TiO.sub.2 Ag/ Te/ Pd/ Ir/ TiO.sub.2
TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO Ag/ Te/ Pd/ Ir/ TiO TiO TiO TiO
Ti.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Ti.sub.2O.sub.3 Ti.sub.2O.sub.3
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Ag/ Te/ Pd/ Ir/ Ti.sub.3O
Ti.sub.3O Ti.sub.3O Ti.sub.3O Ti.sub.2O Ag/ Te/ Pd/ Ir/ Ti.sub.2O
Ti.sub.2O Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Ag/ Te/ Pd/ Ir/
Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.3O.sub.5
Ti.sub.4O.sub.7 Ag/ Te/ Pd/ Ir/ Ti.sub.4O.sub.7 Ti.sub.4O.sub.7
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Ag/ Te/ Pd/ Ir/ ZrO.sub.2
ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 HfO.sub.2 Ag/ Te/ Pd/ Ir/ HfO.sub.2
HfO.sub.2 HfO.sub.2 HfO.sub.2 VO Ag/ Te/ Pd/ Ir/ VO VO VO VO
V.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ V.sub.2O.sub.3 V.sub.2O.sub.3
V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Ag/ Te/ Pd/ Ir/ VO.sub.2
VO.sub.2 VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Ag/ Te/ Pd/ Ir/
V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5 V.sub.2O.sub.5
V.sub.3O.sub.7 Ag/ Te/ Pd/ Ir/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.3O.sub.7 V.sub.3O.sub.7 V.sub.4O.sub.9 Ag/ Te/ Pd/ Ir/
V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Ag/ Te/ Pd/ Ir/ V.sub.6O.sub.13 V.sub.6O.sub.13
V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Ag/ Te/ Pd/ Ir/ NbO NbO NbO NbO
NbO.sub.2 Ag/ Te/ Pd/ Ir/ NbO.sub.2 NbO.sub.2 NbO.sub.2 NbO.sub.2
Nb.sub.2O.sub.5 Ag/ Te/ Pd/ Ir/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5
Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Ag/ Te/ Pd/ Ir/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.8O.sub.19
Nb.sub.16O.sub.38 Ag/ Te/ Pd/ Ir/ Nb.sub.16O.sub.38
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.16O.sub.38
Nb.sub.12O.sub.29 Ag/ Te/ Pd/ Ir/ Nb.sub.12O.sub.29
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.12O.sub.29
Nb.sub.47O.sub.116 Ag/ Te/ Pd/ Ir/ Nb.sub.47O.sub.116
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Nb.sub.47O.sub.116
Ta.sub.2O.sub.5 Ag/ Te/ Pd/ Ir/ Ta.sub.2O.sub.5 Ta.sub.2O.sub.5
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Ag/ Te/ Pd/ Ir/ CrO CrO CrO CrO
Cr.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3
Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Ag/ Te/ Pd/ Ir/ CrO.sub.2
CrO.sub.2 CrO.sub.2 CrO.sub.2 CrO.sub.3 Ag/ Te/ Pd/ Ir/ CrO.sub.3
CrO.sub.3 CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21 Ag/ Te/ Pd/ Ir/
Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 Cr.sub.8O.sub.21
MoO.sub.2 Ag/ Te/ Pd/ Ir/ MoO.sub.2 MoO.sub.2 MoO.sub.2 MoO.sub.2
MoO.sub.3 Ag/ Te/ Pd/ Ir/ MoO.sub.3 MoO.sub.3 MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/ W.sub.2O.sub.3 W.sub.2O.sub.3
W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Ag/ Te/ Pd/ Ir/ WoO.sub.2
WoO.sub.2 WoO.sub.2 WoO.sub.2 WoO.sub.3 Ag/ Te/ Pd/ Ir/ WoO.sub.3
WoO.sub.3 WoO.sub.3 WoO.sub.3 MnO Ag/ Te/ Pd/ Ir/ MnO MnO MnO MnO
Mn/Mg/O Ag/ Te/ Pd/ Ir/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O
Mn.sub.3O.sub.4 Ag/ Te/ Pd/ Ir/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4
Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Ag/ Te/ Pd/ Ir/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 Mn.sub.2O.sub.3
MnO.sub.2 Ag/ Te/ Pd/ Ir/ MnO.sub.2 MnO.sub.2 MnO.sub.2 MnO.sub.2
Mn.sub.2O.sub.7 Ag/ Te/ Pd/ Ir/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
Mn.sub.2O.sub.7 Mn.sub.2O.sub.7 ReO.sub.2 Ag/ Te/ Pd/ Ir/ ReO.sub.2
ReO.sub.2 ReO.sub.2 ReO.sub.2 ReO.sub.3 Ag/ Te/ Pd/ Ir/ ReO.sub.3
ReO.sub.3 ReO.sub.3 ReO.sub.3 Re.sub.2O.sub.7 Ag/ Te/ Pd/ Ir/
Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Ag/ Te/ Pd/ Ir/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Ag/ Te/ Pd/ Ir/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Ag/ Te/ Pd/ Ir/ NaWO.sub.4
NaWO.sub.4 NaWO.sub.4 NaWO.sub.4 Mg.sub.6MnO.sub.8 Ag/ Te/ Pd/ Ir/
Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mg.sub.6MnO.sub.8 Mn.sub.2O.sub.4 Ag/ Te/ Pd/ Ir/ Mn.sub.2O.sub.4
Mn.sub.2O.sub.4 Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6--MnO.sub.8 Ag/ Te/ Pd/ Ir/ (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Ag/ Te/ Pd/ Ir/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Ag/
Te/ Pd/ Ir/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mo.sub.2O.sub.8
Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Ag/ Te/ Pd/ Ir/
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4 Na.sub.2WO.sub.4
Ag/ Te/ Pd/ Ir/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Na.sub.2WO.sub.4 Zr.sub.2Mo.sub.2O.sub.8 Ag/ Te/ Pd/ Ir/
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Ag/
Te/ Pd/ Ir/ MgO NaMnO.sub.4--/ NaMnO.sub.4--/ NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Ag/ Te/
Pd/ Ir/ Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Ag/ Te/ Pd/ Ir/ La.sub.3NdO.sub.6
La.sub.3NdO.sub.6 La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Ag/ Te/ Pd/ Ir/ LaNd.sub.3O.sub.6
LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Ag/ Te/ Pd/ Ir/
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 Ag/ Te/ Pd/ Ir/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Ag/ Te/ Pd/ Ir/
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 Ag/ Te/ Pd/ Ir/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Ag/ Te/ Pd/ Ir/
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Ag/
Te/ Pd/ Ir/ Y--La Y--La Y--La Y--La Zr--La Ag/ Te/ Pd/ Ir/ Zr--La
Zr--La Zr--La Zr--La Pr--La Ag/ Te/ Pd/ Ir/ Pr--La Pr--La Pr--La
Pr--La Ce--La Ag/ Te/ Pd/ Ir/ Ce--La Ce--La Ce--La Ce--La
TABLE-US-00008 TABLE 8 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) Dop NW Mn Ti Li.sub.2O Mn/ Ti/ Li.sub.2O Li.sub.2O Na.sub.2O
Mn/ Ti/ Na.sub.2O Na.sub.2O K.sub.2O Mn/ Ti/ K.sub.2O K.sub.2O
Rb.sub.2O Mn/ Ti/ Rb.sub.2O Rb.sub.2O Cs.sub.2O Mn/ Ti/ Cs.sub.2O
Cs.sub.2O BeO Mn/ Ti/ BeO BeO MgO Mn/ Ti/ MgO MgO CaO Mn/ Ti/ CaO
CaO SrO Mn/ Ti/ SrO SrO BaO Mn/ Ti/ BaO BaO Sc.sub.2O.sub.3 Mn/ Ti/
Sc.sub.2O.sub.3 Sc.sub.2O.sub.3 Y.sub.2O.sub.3 Mn/ Ti/
Y.sub.2O.sub.3 Y.sub.2O.sub.3 La.sub.2O.sub.3 Mn/ Ti/
La.sub.2O.sub.3 La.sub.2O.sub.3 CeO.sub.2 Mn/ Ti/ CeO.sub.2
CeO.sub.2 Ce.sub.2O.sub.3 Mn/ Ti/ Ce.sub.2O.sub.3 Ce.sub.2O.sub.3
Pr.sub.2O.sub.3 Mn/ Ti/ Pr.sub.2O.sub.3 Pr.sub.2O.sub.3
Nd.sub.2O.sub.3 Mn/ Ti/ Nd.sub.2O.sub.3 Nd.sub.2O.sub.3
Sm.sub.2O.sub.3 Mn/ Ti/ Sm.sub.2O.sub.3 Sm.sub.2O.sub.3
Eu.sub.2O.sub.3 Mn/ Ti/ Eu.sub.2O.sub.3 Eu.sub.2O.sub.3
Gd.sub.2O.sub.3 Mn/ Ti/ Gd.sub.2O.sub.3 Gd.sub.2O.sub.3
Tb.sub.2O.sub.3 Mn/ Ti/ Tb.sub.2O.sub.3 Tb.sub.2O.sub.3 TbO.sub.2
Mn/ Ti/ TbO.sub.2 TbO.sub.2 Tb.sub.6O.sub.11 Mn/ Ti/
Tb.sub.6O.sub.11 Tb.sub.6O.sub.11 Dy.sub.2O.sub.3 Mn/ Ti/
Dy.sub.2O.sub.3 Dy.sub.2O.sub.3 Ho.sub.2O.sub.3 Mn/ Ti/
Ho.sub.2O.sub.3 Ho.sub.2O.sub.3 Er.sub.2O.sub.3 Mn/ Ti/
Er.sub.2O.sub.3 Er.sub.2O.sub.3 Tm.sub.2O.sub.3 Mn/ Ti/
Tm.sub.2O.sub.3 Tm.sub.2O.sub.3 Yb.sub.2O.sub.3 Mn/ Ti/
Yb.sub.2O.sub.3 Yb.sub.2O.sub.3 Lu.sub.2O.sub.3 Mn/ Ti/
Lu.sub.2O.sub.3 Lu.sub.2O.sub.3 Ac.sub.2O.sub.3 Mn/ Ti/
Ac.sub.2O.sub.3 Ac.sub.2O.sub.3 Th.sub.2O.sub.3 Mn/ Ti/
Th.sub.2O.sub.3 Th.sub.2O.sub.3 ThO.sub.2 Mn/ Ti/ ThO.sub.2
ThO.sub.2 Pa.sub.2O.sub.3 Mn/ Ti/ Pa.sub.2O.sub.3 Pa.sub.2O.sub.3
PaO.sub.2 Mn/ Ti/ PaO.sub.2 PaO.sub.2 TiO.sub.2 Mn/ Ti/ TiO.sub.2
TiO.sub.2 TiO Mn/ Ti/ TiO TiO Ti.sub.2O.sub.3 Mn/ Ti/
Ti.sub.2O.sub.3 Ti.sub.2O.sub.3 Ti.sub.3O Mn/ Ti/ Ti.sub.3O
Ti.sub.3O Ti.sub.2O Mn/ Ti/ Ti.sub.2O Ti.sub.2O Ti.sub.3O.sub.5 Mn/
Ti/ Ti.sub.3O.sub.5 Ti.sub.3O.sub.5 Ti.sub.4O.sub.7 Mn/ Ti/
Ti.sub.4O.sub.7 Ti.sub.4O.sub.7 ZrO.sub.2 Mn/ Ti/ ZrO.sub.2
ZrO.sub.2 HfO.sub.2 Mn/ Ti/ HfO.sub.2 HfO.sub.2 VO Mn/ Ti/ VO VO
V.sub.2O.sub.3 Mn/ Ti/ V.sub.2O.sub.3 V.sub.2O.sub.3 VO.sub.2 Mn/
Ti/ VO.sub.2 VO.sub.2 V.sub.2O.sub.5 Mn/ Ti/ V.sub.2O.sub.5
V.sub.2O.sub.5 V.sub.3O.sub.7 Mn/ Ti/ V.sub.3O.sub.7 V.sub.3O.sub.7
V.sub.4O.sub.9 Mn/ Ti/ V.sub.4O.sub.9 V.sub.4O.sub.9
V.sub.6O.sub.13 Mn/ Ti/ V.sub.6O.sub.13 V.sub.6O.sub.13 NbO Mn/ Ti/
NbO NbO NbO.sub.2 Mn/ Ti/ NbO.sub.2 NbO.sub.2 Nb.sub.2O.sub.5 Mn/
Ti/ Nb.sub.2O.sub.5 Nb.sub.2O.sub.5 Nb.sub.8O.sub.19 Mn/ Ti/
Nb.sub.8O.sub.19 Nb.sub.8O.sub.19 Nb.sub.16O.sub.38 Mn/ Ti/
Nb.sub.16O.sub.38 Nb.sub.16O.sub.38 Nb.sub.12O.sub.29 Mn/ Ti/
Nb.sub.12O.sub.29 Nb.sub.12O.sub.29 Nb.sub.47O.sub.116 Mn/ Ti/
Nb.sub.47O.sub.116 Nb.sub.47O.sub.116 Ta.sub.2O.sub.5 Mn/ Ti/
Ta.sub.2O.sub.5 Ta.sub.2O.sub.5 CrO Mn/ Ti/ CrO CrO Cr.sub.2O.sub.3
Mn/ Ti/ Cr.sub.2O.sub.3 Cr.sub.2O.sub.3 CrO.sub.2 Mn/ Ti/ CrO.sub.2
CrO.sub.2 CrO.sub.3 Mn/ Ti/ CrO.sub.3 CrO.sub.3 Cr.sub.8O.sub.21
Mn/ Ti/ Cr.sub.8O.sub.21 Cr.sub.8O.sub.21 MoO.sub.2 Mn/ Ti/
MoO.sub.2 MoO.sub.2 MoO.sub.3 Mn/ Ti/ MoO.sub.3 MoO.sub.3
W.sub.2O.sub.3 Mn/ Ti/ W.sub.2O.sub.3 W.sub.2O.sub.3 WoO.sub.2 Mn/
Ti/ WoO.sub.2 WoO.sub.2 WoO.sub.3 Mn/ Ti/ WoO.sub.3 WoO.sub.3 MnO
Mn/ Ti/ MnO MnO Mn/Mg/O Mn/ Ti/ Mn/Mg/O Mn/Mg/O Mn.sub.3O.sub.4 Mn/
Ti/ Mn.sub.3O.sub.4 Mn.sub.3O.sub.4 Mn.sub.2O.sub.3 Mn/ Ti/
Mn.sub.2O.sub.3 Mn.sub.2O.sub.3 MnO.sub.2 Mn/ Ti/ MnO.sub.2
MnO.sub.2 Mn.sub.2O.sub.7 Mn/ Ti/ Mn.sub.2O.sub.7 Mn.sub.2O.sub.7
ReO.sub.2 Mn/ Ti/ ReO.sub.2 ReO.sub.2 ReO.sub.3 Mn/ Ti/ ReO.sub.3
ReO.sub.3 Re.sub.2O.sub.7 Mn/ Ti/ Re.sub.2O.sub.7 Re.sub.2O.sub.7
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mn/ Ti/
Mg.sub.3Mn.sub.3--B.sub.2O.sub.10 Mg.sub.3Mn.sub.3--B.sub.2O.sub.10
Mg.sub.3(BO.sub.3).sub.2 Mn/ Ti/ Mg.sub.3(BO.sub.3).sub.2
Mg.sub.3(BO.sub.3).sub.2 NaWO.sub.4 Mn/ Ti/ NaWO.sub.4 NaWO.sub.4
Mg.sub.6MnO.sub.8 Mn/ Ti/ Mg.sub.6MnO.sub.8 Mg.sub.6MnO.sub.8
Mn.sub.2O.sub.4 Mn/ Ti/ Mn.sub.2O.sub.4 Mn.sub.2O.sub.4
(Li,Mg).sub.6--MnO.sub.8 Mn/ Mn/ (Li,Mg).sub.6--MnO.sub.8
(Li,Mg).sub.6--MnO.sub.8 Na.sub.4P.sub.2O.sub.7 Mn/ Ti/
Na.sub.4P.sub.2O.sub.7 Na.sub.4P.sub.2O.sub.7 Mo.sub.2O.sub.8 Mn/
Ti/ Mo.sub.2O.sub.8 Mo.sub.2O.sub.8 Mn.sub.3O.sub.4/WO.sub.4 Mn/
Ti/ Mn.sub.3O.sub.4/WO.sub.4 Mn.sub.3O.sub.4/WO.sub.4
Na.sub.2WO.sub.4 Mn/ Ti/ Na.sub.2WO.sub.4 Na.sub.2WO.sub.4
Zr.sub.2Mo.sub.2O.sub.8 Mn/ Ti/ Zr.sub.2Mo.sub.2O.sub.8
Zr.sub.2Mo.sub.2O.sub.8 NaMnO.sub.4--/ Mn/ Ti/ MgO NaMnO.sub.4--/
NaMnO.sub.4--/ MgO MgO Na.sub.10Mn--W.sub.5O.sub.17 Mn/ Ti/
Na.sub.10Mn--W.sub.5O.sub.17 Na.sub.10Mn--W.sub.5O.sub.17
La.sub.3NdO.sub.6 Mn/ Ti/ La.sub.3NdO.sub.6 La.sub.3NdO.sub.6
LaNd.sub.3O.sub.6 Mn/ Ti/ LaNd.sub.3O.sub.6 LaNd.sub.3O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 Mn/ Ti/ La.sub.1,5Nd.sub.2,5O.sub.6
La.sub.1,5Nd.sub.2,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6 Mn/ Ti/
La.sub.2,5Nd.sub.1,5O.sub.6 La.sub.2,5Nd.sub.1,5O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 Mn/ Ti/ La.sub.3,2Nd.sub.0,8O.sub.6
La.sub.3,2Nd.sub.0,8O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6 Mn/ Ti/
La.sub.3,5Nd.sub.0,5O.sub.6 La.sub.3,5Nd.sub.0,5O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Mn/ Ti/ La.sub.3,8Nd.sub.0,2O.sub.6
La.sub.3,8Nd.sub.0,2O.sub.6 Y--La Mn/ Ti/ Y--La Y--La Zr--La Mn/
Ti/ Zr--La Zr--La Pr--La Mn/ Ti/ Pr--La Pr--La Ce--La Mn/ Ti/
Ce--La Ce--La
TABLE-US-00009 TABLE 9 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) NW Dop La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Eu/Na Eu/Na/
Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Na Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Na/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/
Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Mg/Na Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/
Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/
Sr/W/ Sr/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Zr Sr/Zr/
Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/ Mg/La/K
Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/K/Mg/Tm Na/K/Mg/Tm/
Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Dy/K Na/Dy/K/ Na/Dy/K/
Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/
Na/La/Dy/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/La/Eu
Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/La/Eu/In Na/La/Eu/In/
Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Ce Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/
Sr/Ce/ Sr/Ce/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/ Na/La/K Na/La/K/ Na/La/K/
Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/La/Li/Cs Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/
Na/La/Li/Cs/ Na/La/Li/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
K/La K/La/ K/La/ K/La/ K/La/ K/La/ K/La/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/ K/La/S/
K/La/S/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 K/Na K/Na/ K/Na/
K/Na/ K/Na/ K/Na/ K/Na/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Li/Cs/La Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/
Li/Cs/La/ Li/Cs/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Cs/La/Tm
Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/
Li/Cs/La/Tm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Tb Sr/Tb/
Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/ Li/Cs/Sr/Tm
Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/
Li/Cs/Sr/Tm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Sr/Cs
Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Sr/Zn/K Li/Sr/Zn/K/
Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/
Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/
Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Li/Na Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Li/Na/Rb/Ga Li/Na/Rb/Ga/ Li/Na/Rb/Ga/
Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/
Li/Na/Sr/ Li/Na/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Na/Sr/La
Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/
Li/Na/Sr/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Sm/Cs
Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ba/Sm/Yb/S Ba/Sm/Yb/S/
Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/
Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/ Ba/Tm/K/La
Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/
Ba/Tm/K/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ba/Tm/Zn/K
Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/
Ba/Tm/Zn/K/ La2O3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Cs/K/La Cs/K/La/ Cs/K/La/
Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Cs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/
Cs/La/Tm/Na/ Cs/La/Tm/Na/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Cs/Li/K/La Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/
Cs/Li/K/La/ Cs/Li/K/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sm/Li/Sr/Cs Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/
Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Cs/La Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/
Sr/Cs/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Tm/Li/Cs
Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/
Sr/Tm/Li/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Zn/K Zn/K/ Zn/K/
Zn/K/ Zn/K/ Zn/K/ Zn/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/
Zr/Cs/K/La/ Zr/Cs/K/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/
Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/
Sr/Ho/Tm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Nd/S La/Nd/S/
La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Li/Rb/Ca Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/
Li/Rb/Ca/ Li/Rb/Ca/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/K Li/K/ Li/K/
Li/K/ Li/K/ Li/K/ Li/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/
Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/
Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/
Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Zr/K Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 Rb/Sr/ Rb/Sr/Lu Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/
Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/Sr/Lu/Nb Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/
Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/Eu/Hf Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/
Na/Eu/Hf/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Dy/Rb/Gd
Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/
Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/
Ca/Cs/ Ca/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ca/Mg/Na
Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/
Hf/Bi/ Hf/Bi/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Sn Sr/Sn/
Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Pr/K Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 Rb/Sr/ Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/
Sr/Nb/ Sr/Nb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Zr/W Zr/W/ Zr/W/
Zr/W/ Zr/W/ Zr/W/ Zr/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Y/W Y/W/ Y/W/ Y/W/ Y/W/ Y/W/ Y/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/W Na/W/ Na/W/ Na/W/ Na/W/ Na/W/ Na/W/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/
Bi/Cs/ Bi/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Bi/Ca Bi/Ca/
Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6
Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Bi/Sb Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/
Ge/Hf/ Ge/Hf/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Hf/Sm Hf/Sm/
Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sb/Bi Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sb/Au Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/
Sb/Au/ Sb/Au/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sb/Sm Sb/Sm/
Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 Rb/Sr/ Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/
Sb/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sb/W Sb/W/ Sb/W/
Sb/W/ Sb/W/ Sb/W/ Sb/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/
Sb/Sn/ Sb/Sn/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Yb/Au Yb/Au/
Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Yb/Ta Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/
Yb/Sr/ Yb/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Yb/Pb Yb/Pb/
Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/
Au/Sr/ Au/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Hf/K Sr/Hf/K/
Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
Rb/Sr/ W/Ge W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/
Ta/Hf/ Ta/Hf/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 W/Au W/Au/ W/Au/
W/Au/ W/Au/ W/Au/ W/Au/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Ca/W Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/
Sm/Li/ Sm/Li/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/K La/K/ La/K/
La/K/ La/K/ La/K/ La/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/
Na/K/Mg/ Na/K/Mg/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Zr/Cs Zr/Cs/
Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/
Na/Li/Cs/ Na/Li/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Sr Li/Sr/
Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/
Sr/Pr/ Sr/Pr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/ Dy/K Dy/K/ Dy/K/ Dy/K/ Dy/K/
Dy/K/ Dy/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Mg La/Mg/
La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/
Na/Nd/In/K/ Na/Nd/In/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
In/Sr In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/
Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/
Ga/Cs/ Ga/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
K/La/Zr/Ag/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Lu/Fe Lu/Fe/
Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/
Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/
Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/
Li/Cs/Tm/ Li/Cs/Tm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Zr/K Zr/K/ Zr/K/
Zr/K/ Zr/K/ Zr/K/ Zr/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/
Sr/Hf/Rb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/
Li/Cs/ Li/Cs/ Li/Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ce/Zr/La Ce/Zr/La/ Ce/Zr/La/
Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Ca/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/
Ca/Al/La/ Ca/Al/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Zn/La
Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/
Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 In/K In/K/ In/K/ In/K/ In/K/
In/K/ In/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ho/Cs/Li/La
Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/
Ho/Cs/Li/La/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Cs/La/Na
Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/S/Sr La/S/Sr/ La/S/Sr/
La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
K/La/Zr/Ag/ K/La/Zr/Ag/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Lu/Tl Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/
Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Na/Sr/Eu/Ca Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/
Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sr/B Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 Rb/Sr/ K/Cs/Sr/La K/Cs/Sr/La/ K/Cs/Sr/La/
K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Na/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/
Na/Sr/Lu/ Na/Sr/Lu/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Eu/Dy
Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Lu/Nb Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/
Lu/Nb/ Lu/Nb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Dy/Gd
La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Mg/Tl/P Na/Mg/Tl/P/
Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/
Na/Pt/ Na/Pt/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Gd/Li/K Gd/Li/K/
Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6
Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/La/Dy/S Sr/La/Dy/S/
Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/
Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Na/Ce Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Ga/Gd/Al Na/Ga/Gd/Al/
Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ba/Rh/Ta Ba/Rh/Ta/ Ba/Rh/Ta/
Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/
Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Cs/Eu/S Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/
Cs/Eu/S/ Cs/Eu/S/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sm/Tm/Yb/Fe
Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/
Sm/Tm/Yb/Fe/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sm/Tm/Yb
Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/
Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Rb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/
Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/
Gd/Ho/Al/P/ Gd/Ho/Al/P/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/
Na/Ca/Lu/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Cu/Sn Cu/Sn/
Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Al/Bi Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/
Al/Mo/ Al/Mo/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Al/Nb Al/Nb/
Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Ga/Bi Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/
Mg/W/ Mg/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Pb/Au Pb/Au/
Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/
Sr/Ta/ Sr/Ta/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Na Na/ Na/ Na/
Na/ Na/ Na/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr Sr/ Sr/ Sr/
Sr/ Sr/ Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ca Ca/ Ca/ Ca/
Ca/ Ca/ Ca/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Yb Yb/ Yb/ Yb/
Yb/ Yb/ Yb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Cs Cs/ Cs/ Cs/
Cs/ Cs/ Cs/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sb Sb/ Sb/ Sb/
Sb/ Sb/ Sb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Gd/Ho Gd/Ho/
Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Ho/Sr Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Gd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/
Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/
Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Na/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/
Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Ho/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/
Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Tm/Na La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/
Sr/W/Li/ Sr/W/Li/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Ca/Sr/W Ca/Sr/W/
Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/
Au/Re/ Au/Re/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Sr/W Sr/W/ Sr/W/
Sr/W/ Sr/W/ Sr/W/ Sr/W/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Ce La/Ce/ La/Ce/ La/Ce/ La/Ce/
La/Ce/ La/Ce/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Sr La/Sr/
La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/
La/Nd/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Bi/Sr
La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Ce/Nd/Sr La/Ce/Nd/Sr/
La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 La/Bi/Ce/Nd/Sr La/Bi/Ce/Nd/Sr/
La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/
La/Bi/Ce/Nd/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Eu/Gd Eu/Gd/
Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/
Eu/Sr/ Eu/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Mg/Sr Mg/Sr/
Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Ce/Mg Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/
Au/Pb/ Au/Pb/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Bi/Hf Bi/Hf/
Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/
La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3
Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Eu/Y Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/
Eu/Y/ Eu/Y/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Mg/Nd Mg/Nd/
Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6
La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La.sub.2O.sub.3
Nd.sub.2O.sub.3 Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3
La.sub.3NdO.sub.6 Mg/Nd/Fe Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/
Mg/Nd/Fe/ Mg/Nd/Fe/ La.sub.2O.sub.3 Nd.sub.2O.sub.3 Yb.sub.2O.sub.3
Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 La.sub.3NdO.sub.6 Rb/Sr Rb/Sr/
Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ La.sub.2O.sub.3 Nd.sub.2O.sub.3
Yb.sub.2O.sub.3 Eu.sub.2O.sub.3 Sm.sub.2O.sub.3 Rb/Sr/
TABLE-US-00010 TABLE 10 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) NW Dop La.sub.4-XNd.sub.XO.sub.6* LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Eu/Na
Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Na Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/
Sr/Na/ Sr/Na/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Zr/Eu/Ca
Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/
Na/Zr/Eu/Ca/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Mg/Na
Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/
Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/W Sr/W/
Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/
Mg/La/K/ Mg/La/K/ Mg/La/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/
Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Dy/K
Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/B Sr/B/
Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/
Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/La/Eu Na/La/Eu/ Na/La/Eu/ Na/La/Eu/
Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/La/Eu/In Na/La/Eu/In/ Na/La/Eu/In/
Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/La/K
Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/La/Li/Cs
Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/
Na/La/Li/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 K/La K/La/
K/La/ K/La/ K/La/ K/La/ K/La/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/
K/La/S/ K/La/S/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 K/Na K/Na/
K/Na/ K/Na/ K/Na/ K/Na/ K/Na/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/
Li/Cs/ Li/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Cs/La
Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Cs/La/Tm
Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/
Li/Cs/La/Tm/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Cs/Sr/Tm
Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/
Li/Cs/Sr/Tm/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Sr/Cs
Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Sr/Zn/K
Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/
Li/Sr/Zn/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Pr
Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/
Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/
Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Na
Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Li/Na/Rb/Ga Li/Na/Rb/Ga/ Li/Na/Rb/Ga/
Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Na/Sr
Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Na/Sr/La
Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/
Li/Na/Sr/La/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Sm/Cs
Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ba/Sm/Yb/S
Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/
Ba/Sm/Yb/S/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ba/Tm/K/La
Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/
Ba/Tm/K/La/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ba/Tm/Zn/K
Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/
Ba/Tm/Zn/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Cs/K/La
Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Pr/K
Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Cs/La/Tm/Na
Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/
Cs/La/Tm/Na/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Cs/Li/K/La
Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/
Cs/Li/K/La/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sm/Li/Sr/Cs
Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/
Sm/Li/Sr/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Cs/La
Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Tm/Li/Cs
Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/
Sr/Tm/Li/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Zn/K Zn/K/
Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/
Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Ca/In/Ni
Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/
Rb/Ca/In/Ni/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Ho/Tm
Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Nd/S
La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Hf/Rb
Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Rb/Ca
Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/K Li/K/
Li/K/ Li/K/ Li/K/ Li/K/ Li/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/
Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Ca/Dy/P
Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/
Rb/Ca/Dy/P/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Mg/La/Yb/Zn
Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/
Mg/La/Yb/Zn/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Sr/Lu
Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Sr/Lu/Nb
Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/
Na/Sr/Lu/Nb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/Eu/Hf Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/
Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/
Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/
Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/
Rb/Hf/ Rb/Hf/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Cs
Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/
Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/
Hf/Bi/ Hf/Bi/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Sn
Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/
Sr/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Nb
Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Zr/W Zr/W/ Zr/W/ Zr/W/ Zr/W/ Zr/W/
Zr/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Hf/K
Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Y/W Y/W/
Y/W/ Y/W/ Y/W/ Y/W/ Y/W/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/W Na/W/ Na/W/ Na/W/ Na/W/ Na/W/
Na/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Bi/W Bi/W/
Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/
Bi/Cs/ Bi/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Bi/Ca
Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/
Bi/Sn/ Bi/Sn/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Bi/Sb
Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/
Ge/Hf/ Ge/Hf/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Hf/Sm
Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/
Sb/Ag/ Sb/Ag/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Bi
Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Au Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/
Sb/Au/ Sb/Au/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Zr
Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Sm Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/
Sb/Sm/ Sb/Sm/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Sr
Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/
Sb/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Hf
Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/
Sb/Yb/ Sb/Yb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sb/Sn
Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/
Yb/Au/ Yb/Au/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Yb/Ta
Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/
Yb/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Yb/Sr
Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Yb/Pb Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/
Yb/Pb/ Yb/Pb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Yb/W Yb/W/
Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/
Yb/Ag/ Yb/Ag/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Au/Sr
Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 W/Ge W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/
W/Ge/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ta/Sr
Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/
Ta/Hf/ Ta/Hf/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 W/Au W/Au/
W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/
Sr/Tb/ Sr/Tb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ca/W Ca/W/
Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/
Au/Re/ Au/Re/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sm/Li
Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 La/K La/K/ La/K/ La/K/ La/K/ La/K/
La/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Zn/Cs
Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/
Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Zr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/
Zr/Cs/ Zr/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Ce
Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/
Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/
Li/Sr/ Li/Sr/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Dy/K
La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Dy/K Dy/K/
Dy/K/ Dy/K/ Dy/K/ Dy/K/ Dy/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/
La/Mg/ La/Mg/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Nd/In/K
Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/
Na/Nd/In/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 In/Sr
In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/
Sr/Cs/ Sr/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Ce
Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/
Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/
Ga/Cs/ Ga/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
K/La/Zr/Ag/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Lu/Fe
Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/
Sr/Tm/ Sr/Tm/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Dy
La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/
Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Zr/K Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/
Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/
Mg/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Rb/Ga
Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/Cs/Tm
Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Zr/K Zr/K/
Zr/K/ Zr/K/ Zr/K/ Zr/K/ Zr/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/
Li/Cs/ Li/Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Li/K/La
Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ce/Zr/La
Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Al/La
Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Zn/La
Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Cs/Zn
Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sm/Cs
Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 In/K In/K/ In/K/ In/K/ In/K/ In/K/
In/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ho/Cs/Li/La
Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/
Ho/Cs/Li/La/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Cs/La/Na
Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/S/Sr
La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
K/La/Zr/Ag/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Lu/Tl
Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/
Pr/Zn/ Pr/Zn/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Sr/La
Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Ce/K
Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Sr/Eu/Ca
Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/
Na/Sr/Eu/Ca/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 K/Cs/Sr/La
K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/
K/Cs/Sr/La/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Sr/Lu
Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Eu/Dy
Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Lu/Nb
Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/
La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/
Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Pt
Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/
Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/
Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/La/Dy/S Sr/La/Dy/S/ Sr/La/Dy/S/
Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Ce/Co
Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Ce
Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/
Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ba/Rh/Ta
Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ba/Ta
Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/
Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Cs/Eu/S Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/
Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/
Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sm/Tm/Yb
Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Hf/Zr/Ta
Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Tb/K
Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Gd/Li/K
Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/
Rb/Gd/Li/K/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Gd/Ho/Al/P
Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/
Gd/Ho/Al/P/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Ca/Lu
Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Cu/Sn
Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/
Ag/Au/ Ag/Au/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Al/Bi
Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/
Al/Mo/ Al/Mo/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Al/Nb
Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/
Au/Pt/ Au/Pt/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ga/Bi
Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/
Mg/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Pb/Au Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/
Pb/Au/ Pb/Au/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sn/Mg
Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/
Zn/Bi/ Zn/Bi/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Ta
Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Na Na/ Na/ Na/ Na/ Na/ Na/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr Sr/ Sr/
Sr/ Sr/ Sr/ Sr/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ca Ca/ Ca/
Ca/ Ca/ Ca/ Ca/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Yb Yb/ Yb/
Yb/ Yb/ Yb/ Yb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Cs Cs/ Cs/
Cs/ Cs/ Cs/ Cs/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sb Sb/ Sb/
Sb/ Sb/ Sb/ Sb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Gd/Ho
Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/
Zr/Bi/ Zr/Bi/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ho/Sr
Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Gd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/
Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/
Ca/Sr/ Ca/Sr/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Sr/W
Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Na/Zr/Eu/Tm
Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/
Na/Zr/Eu/Tm/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Ho/Tm/Na
Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/
Sr/Ho/Tm/Na/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Pb
Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/
Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/
Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/
Sr/Hf/ Sr/Hf/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Au/Re
Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/
Sr/W/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Nd
La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/
La/Sm/ La/Sm/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Ce
La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/
La/Sr/ La/Sr/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Nd/Sr
La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Bi/Sr
La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 La/Ce/Nd/Sr
La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/
La/Ce/Nd/Sr/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6
La/Bi/Ce/Nd/Sr La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/
La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Eu/Gd
Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/
Ca/Na/ Ca/Na/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Eu/Sm
Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/
Eu/Sr/ Eu/Sr/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Mg/Sr
Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Ce/Mg Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/
Ce/Mg/ Ce/Mg/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Gd/Sm
Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/
Au/Pb/ Au/Pb/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Bi/Hf
Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/
Rb/S/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Sr/Nd
Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 Eu/Y Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/
Eu/Y/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Mg/Nd
Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/
La/Mg/ La/Mg/ La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Mg/Nd/Fe
Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/
La.sub.4-XNd.sub.XO.sub.6 LaNd.sub.3O.sub.6
La.sub.1.5Nd.sub.2.5O.sub.6 La.sub.2.5Nd.sub.1.5O.sub.6
La.sub.3.2Nd.sub.0.8O.sub.6 La.sub.3.5Nd.sub.0.5O.sub.6 Rb/Sr
Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ La.sub.4-XNd.sub.XO.sub.6
LaNd.sub.3O.sub.6 La.sub.1.5Nd.sub.2.5O.sub.6
La.sub.2.5Nd.sub.1.5O.sub.6 La.sub.3.2Nd.sub.0.8O.sub.6
La.sub.3.5Nd.sub.0.5O.sub.6 *x is a number ranging from greater
than 0 to less than 4
TABLE-US-00011 TABLE 11 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) NW Dop La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Eu/Na Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Na Sr/Na/
Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Na/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/
Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--Laa Ce--La Mg/Na Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/
Mg/Na/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/
Sr/Sm/Ho/Tm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/
Mg/La/K/ Mg/La/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La Na/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/
Na/K/Mg/Tm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Na/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/La/Dy
Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/La/Eu
Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/La/Eu/In
Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/La/K
Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/La/Li/Cs
Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La K/La K/La/
K/La/ K/La/ K/La/ K/La/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/ K/La/S/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La K/Na K/Na/
K/Na/ K/Na/ K/Na/ K/Na/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Cs/La
Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Pr/K
Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Cs/La/Tm
Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Cs/Sr/Tm
Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Sr/Cs
Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Sr/Zn/K
Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Ga/Cs
Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/K/Sr/La
Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Na Li/Na/
Li/Na/ Li/Na/ Li/Na/ Li/Na/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Li/Na/Rb/Ga Li/Na/Rb/Ga/ Li/Na/Rb/Ga/
Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/
Li/Na/Sr/ Li/Na/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La Li/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/
Li/Na/Sr/La/ Li/Na/Sr/La/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Li/Sm/Cs Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/
Li/Sm/Cs/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/
Ba/Sm/Yb/S/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ba/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/
Ba/Tm/K/La/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/
Ba/Tm/Zn/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La C + s/K/La
Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Cs/La/Tm/Na
Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Cs/Li/K/La
Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sm/Li/Sr/Cs
Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Cs/La
Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Tm/Li/Cs
Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Zn/K Zn/K/
Zn/K/ Zn/K/ Zn/K/ Zn/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/
Zr/Cs/K/La/ Zr/Cs/K/La/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/
Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Sr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/
Sr/Ho/Tm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
La/Nd/S La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Rb/Ca
Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/K Li/K/
Li/K/ Li/K/ Li/K/ Li/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/
Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/
Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/
Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Rb/Sr/Lu Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/
Rb/Sr/Lu/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sr/B Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La Na/Sr/Lu/Nb Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/
Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La Na/Eu/Hf Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/
Na/Eu/Hf/ Na/Eu/Hf/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Pt/Bi
Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Rb/Hf Rb/Hf/
Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ca/Mg/Na
Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Hf/Bi Hf/Bi/
Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/W Sr/W/
Sr/W/ Sr/W/ Sr/W/ Sr/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Zr/W Zr/W/
Zr/W/ Zr/W/ Zr/W/ Zr/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Y/W Y/W/ Y/W/ Y/W/ Y/W/ Y/W/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/W Na/W/
Na/W/ Na/W/ Na/W/ Na/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Bi/Cs Bi/Cs/
Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Bi/Ca Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Pr Sr/Pr/
Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Bi/Sb Bi/Sb/
Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Hf/Sm Hf/Sm/
Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sb/Bi Sb/Bi/
Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sb/Au Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sb/Sm Sb/Sm/
Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sb/W Sb/W/
Sb/W/ Sb/W/ Sb/W/ Sb/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sb/Yb Sb/Yb/
Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Hf/K Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/
Sr/Hf/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Yb/Au Yb/Au/
Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Yb/Ta Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Yb/W Yb/W/
Yb/W/ Yb/W/ Yb/W/ Yb/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Yb/Pb Yb/Pb/
Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Yb/Ag Yb/Ag/
Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La W/Ge W/Ge/
W/Ge/ W/Ge/ W/Ge/ W/Ge/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/
Sr/Hf/Rb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ta/Hf Ta/Hf/
Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La W/Au W/Au/ W/Au/ W/Au/ W/Au/ W/Au/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ca/W Ca/W/
Ca/W/ Ca/W/ Ca/W/ Ca/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sm/Li Sm/Li/
Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La La/K La/K/ La/K/ La/K/ La/K/ La/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Zn/Cs Zn/Cs/
Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/
Na/K/Mg/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Zr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ca/Ce Ca/Ce/
Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Zr/K Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/
Sr/Zr/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Li/Sr Li/Sr/
Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/
La/Dy/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Dy/K Dy/K/ Dy/K/ Dy/K/ Dy/K/ Dy/K/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Nd/In/K
Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La In/Sr In/Sr/
In/Sr/ In/Sr/ In/Sr/ In/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/
Rb/Ga/Tm/Cs/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Zr Sr/Zr/
Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Lu/Fe Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Tm Sr/Tm/
Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sm/Li/Sr
Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Mg/K Mg/K/
Mg/K/ Mg/K/ Mg/K/ Mg/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/
Li/Rb/Ga/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Zr/K Zr/K/
Zr/K/ Zr/K/ Zr/K/ Zr/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Ce Sr/Ce/
Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/
Li/K/La/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ce/Zr/La Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ca/Al/La
Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Zn/La
Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Cs/Zn
Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sm/Cs Sm/Cs/
Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La In/K In/K/ In/K/ In/K/ In/K/ In/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ho/Cs/Li/La
Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Cs/La/Na
Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La La/S/Sr
La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Lu/Tl Lu/Tl/
Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Rb/Sr/La
Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Sr/Eu/Ca
Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La K/Cs/Sr/La
K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Sr/Lu
Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Eu/Dy
Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Lu/Nb Lu/Nb/
Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La La/Dy/Gd
La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Mg/Tl/P
Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Pt Na/Pt/
Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/
Gd/Li/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/La/Dy/S
Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Ce/Co
Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Ce Na/Ce/
Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/
Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La Ba/Rh/Ta Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/
Ba/Rh/Ta/ Ba/Rh/Ta/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Al/Bi
Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Cs/Eu/S
Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sm/Tm/Yb/Fe
Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sm/Tm/Yb
Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Hf/Zr/Ta
Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Rb/Gd/Li/K
Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--Lai/K Ce--La
Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/
Gd/Ho/Al/P/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Cu/Sn Cu/Sn/
Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Al/Bi Al/Bi/
Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Al/Nb Al/Nb/
Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/
Sr/Ce/K/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ga/Bi Ga/Bi/
Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Pb/Au Pb/Au/
Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Zn/Bi Zn/Bi/
Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na Na/ Na/
Na/ Na/ Na/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sr Sr/ Sr/ Sr/ Sr/ Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Ca Ca/ Ca/ Ca/ Ca/ Ca/ La.sub.3.8Nd.sub.0.2O.sub.6
Y--La Zr--La Pr--La Ce--La Yb Yb/ Yb/ Yb/ Yb/ Yb/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Cs Cs/ Cs/
Cs/ Cs/ Cs/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Sb Sb/ Sb/ Sb/ Sb/ Sb/ La.sub.3.8Nd.sub.0.2O.sub.6/ Y--La/ Zr--La/
Pr--La/ Ce--La/ Zn/Bi Zn/Bi Zn/Bi Zn/Bi Zn/Bi Gd/Ho Gd/Ho/ Gd/Ho/
Gd/Ho/ Gd/Ho/ Gd/Ho/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ho/Sr Ho/Sr/
Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Gd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/
Gd/Ho/Sr/ Gd/Ho/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ca/Sr/W
Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Na/Zr/Eu/Tm
Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Ho/Tm/Na
Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Pb Sr/Pb/
Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/
Sr/W/Li/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/Hf Sr/Hf/
Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Sr/W Sr/W/
Sr/W/ Sr/W/ Sr/W/ Sr/W/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La La/Sm La/Sm/
La/Sm/ La/Sm/ La/Sm/ La/Sm/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La La/Ce La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La La/Sr La/Sr/
La/Sr/ La/Sr/ La/Sr/ La/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/
La/Nd/Sr/ La/Nd/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La La/Ce/Nd/Sr
La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
La/Bi/Ce/Nd/Sr La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/
La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Eu/Gd Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ca/Na Ca/Na/
Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Eu/Sr Eu/Sr/
Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Mg/Sr Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Ce/Mg Ce/Mg/
Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Au/Pb Au/Pb/
Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La
Zr--La Pr--La Ce--La Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Rb/S Rb/S/
Rb/S/ Rb/S/ Rb/S/ Rb/S/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La Eu/Y Eu/Y/
Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La
Pr--La Ce--La Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La La/Mg La/Mg/
La/Mg/ La/Mg/ La/Mg/ La/Mg/ La.sub.3.8Nd.sub.0.2O.sub.6 N Y--La
Zr--La Pr--La Ce--La Mg/Nd/Fe Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/
Mg/Nd/Fe/ Mg/Nd/Fe/ La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La
Ce--La Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/
La.sub.3.8Nd.sub.0.2O.sub.6 Y--La Zr--La Pr--La Ce--La
TABLE-US-00012 TABLE 12 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS
(DOP) NW Dop Ln1.sub.4-xLn2.sub.xO.sub.6*
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Eu/Na Eu/Na/ Eu/Na/
Eu/Na/ Eu/Na/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Na Sr/Na/ Sr/Na/
Sr/Na/ Sr/Na/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Na/Zr/Eu/Ca
Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/Na Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/
Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/W Sr/W/ Sr/W/
Sr/W/ Sr/W/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/
Na/K/Mg/Tm/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/La/Eu Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/La/Eu/In Na/La/Eu/In/ Na/La/Eu/In/
Na/La/Eu/In/ Na/La/Eu/In/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Na/La/K Na/La/K/
Na/La/K/ Na/La/K/ Na/La/K/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Na/La/Li/Cs
Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO K/La K/La/ K/La/ K/La/ K/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO K/Na K/Na/ K/Na/ K/Na/ K/Na/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Cs/La Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Cs/La/Tm Li/Cs/La/Tm/ Li/Cs/La/Tm/
Li/Cs/La/Tm/ Li/Cs/La/Tm/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Li/Cs/Sr/Tm
Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/
Li/Sr/Zn/K/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/
Li/K/Sr/La/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Na Li/Na/ Li/Na/ Li/Na/ Li/Na/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Na/Rb/Ga Li/Na/Rb/Ga/ Li/Na/Rb/Ga/
Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Zr Sr/Zr/ Sr/Zr/
Sr/Zr/ Sr/Zr/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Li/Na/Sr Li/Na/Sr/
Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Li/Na/Sr/La
Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Sm/Cs Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/
Ba/Sm/Yb/S/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ba/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/
Ba/Tm/K/La/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/
Ba/Tm/Zn/K/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Cs/K/La Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Cs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/
Cs/La/Tm/Na/ Cs/La/Tm/Na/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Cs/Li/K/La
Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sm/Li/Sr/Cs Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/
Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Cs/La Sr/Cs/La/
Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Tm/Li/Cs
Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/
Zr/Cs/K/La/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/
Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Ho/Tm Sr/Ho/Tm/
Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO La/Nd/S La/Nd/S/
La/Nd/S/ La/Nd/S/ La/Nd/S/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Tb Sr/Tb/ Sr/Tb/
Sr/Tb/ Sr/Tb/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Li/Rb/Ca Li/Rb/Ca/
Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Li/K Li/K/ Li/K/
Li/K/ Li/K/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/
Tm/Lu/Ta/P/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/
Rb/Ca/Dy/P/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/
Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Rb/Sr/Lu Rb/Sr/Lu/
Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Na/Sr/Lu/Nb
Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Eu/Hf Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zr/W Zr/W/ Zr/W/ Zr/W/ Zr/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Y/W Y/W/ Y/W/ Y/W/ Y/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/W Na/W/ Na/W/ Na/W/ Na/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Ce Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Bi/Ca Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Bi/Sb Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/Bi Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/Au Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/Sm Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO
Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Pr/K Sr/Pr/K/
Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sb/Sn Sb/Sn/ Sb/Sn/
Sb/Sn/ Sb/Sn/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Yb/Au Yb/Au/ Yb/Au/
Yb/Au/ Yb/Au/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Yb/Ta Yb/Ta/ Yb/Ta/
Yb/Ta/ Yb/Ta/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Yb/W Yb/W/ Yb/W/
Yb/W/ Yb/W/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Yb/Pb Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO W/Ge W/Ge/ W/Ge/ W/Ge/ W/Ge/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO W/Au W/Au/ W/Au/ W/Au/ W/Au/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/W Ca/W/ Ca/W/ Ca/W/ Ca/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/K La/K/ La/K/ La/K/ La/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Zr/K Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Dy/K Dy/K/ Dy/K/ Dy/K/ Dy/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/
Na/Nd/In/K/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO In/Sr In/Sr/ In/Sr/ In/Sr/ In/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/
Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Ga/Cs Ga/Cs/ Ga/Cs/
Ga/Cs/ Ga/Cs/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Lu/Fe Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zr/K Zr/K/ Zr/K/ Zr/K/ Zr/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ce/Zr/La Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Zn/La Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO In/K In/K/ In/K/ In/K/ In/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/
Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Cs/La/Na Cs/La/Na/
Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO La/S/Sr La/S/Sr/
La/S/Sr/ La/S/Sr/ La/S/Sr/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO K/La/Zr/Ag
K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Lu/Tl Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Sr/Eu/Ca Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/
Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO K/Cs/Sr/La
K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Lu/Nb Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/
Na/Mg/Tl/P/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/La/Dy/S Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/
Sr/La/Dy/S/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Ce Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/
Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Ba/Rh/Ta Ba/Rh/Ta/
Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Ba/Ta Ba/Ta/ Ba/Ta/
Ba/Ta/ Ba/Ta/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Na/Al/Bi Na/Al/Bi/
Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Cs/Eu/S Cs/Eu/S/
Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sm/Tm/Yb/Fe
Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/
Rb/Gd/Li/K/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/
Gd/Ho/Al/P/ Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO
Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Cu/Sn Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Al/Bi Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ga/Bi Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Pb/Au Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na Na/ Na/ Na/ Na/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr Sr/ Sr/ Sr/ Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca Ca/ Ca/ Ca/ Ca/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Yb Yb/ Yb/ Yb/ Yb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Cs Cs/ Cs/ Cs/ Cs/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sb Sb/ Sb/ Sb/ Sb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ho/Sr Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/B Sr/B/ Sr/B/ Sr/B/ Sr/B/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Gd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Na/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/
Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO Sr/Ho/Tm/Na
Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Ce La/Ce/ La/Ce/ La/Ce/ La/Ce/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Ce/Nd/Sr La/Ce/Nd/Sr/ La/Ce/Nd/Sr/
La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ Ln1.sub.4-xLn2.sub.xO.sub.6
La.sub.4-xLn1.sub.xO.sub.6 Y.sub.2O.sub.3 MgO La/Bi/Ce/Nd/Sr
La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Eu/Gd Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/Sr Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Ce/Mg Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Eu/Y Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Sr/Hf/K Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Mg/Nd/Fe Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/
Ln1.sub.4-xLn2.sub.xO.sub.6 La.sub.4-xLn1.sub.xO.sub.6
Y.sub.2O.sub.3 MgO *Ln1 and Ln2 are each independently a lanthanide
element, wherein Ln1 and Ln2 are not the same and x is a number
ranging from greater than 0 to less than 4
[0311] composition represented by E.sup.1/E.sup.2/E.sup.3 etc.,
wherein E.sup.1, E.sup.2 and E.sup.3 are each independently an
element or a compound comprising one or more elements, refers to a
nanowire composition comprised of a mixture of E.sup.1, E.sup.2 and
E.sup.3. E.sup.1/E.sup.2/E.sup.3 etc. are not necessarily present
in equal amounts and need not form a bond with one another. For
example, a nanowire comprising Li/MgO refers to a nanowire
comprising Li and MgO, for example, Li/MgO may refer to a MgO
nanowire doped with Li. By way of another example, a nanowire
comprising NaMnO.sub.4/MgO refers to a nanowire comprised of a
mixture of NaMnO.sub.4 and MgO. Dopants may be added in suitable
form. For example in a lithium doped magnesium oxide nanowire
(Li/MgO), the Li dopant can be incorporated in the form of
Li.sub.2O, Li.sub.2CO.sub.3, LiOH, or other suitable forms. Li may
be fully incorporated in the MgO crystal lattice (e.g., (Li,Mg)O)
as well. Dopants for other nanowires may be incorporated
analogously.
[0312] In some more specific embodiments, the dopant is selected
from Li, Ba and Sr. In other specific embodiments, the nanowires
comprise Li/MgO, Ba/MgO, Sr/La.sub.2O.sub.3, Ba/La.sub.2O.sub.3,
Mn/Na.sub.2WO.sub.4, Mn.sub.2O.sub.3/Na.sub.2WO.sub.4,
Mn.sub.3O.sub.4/Na.sub.2WO.sub.4, Mg.sub.6MnO.sub.8,
Li/B/Mg.sub.6MnO.sub.8, Na/B/Mg.sub.6MnO.sub.8,
Zr.sub.2Mo.sub.2O.sub.8 or NaMnO.sub.4/MgO.
[0313] In some other specific embodiments, the nanowire comprises a
mixed oxide of Mn and Mg with or without B and with or without Li.
Additional dopants for such nanowires may comprise doping elements
selected from Group 1 and 2 and groups 7-13. The dopants may be
present as single dopants or in combination with other dopants. In
certain specific embodiments of nanowires comprising a mixed oxide
of Mn and Mg with or without B and with or without Li., the dopant
comprises a combination of elements from group 1 and group
8-11.
[0314] Nanowires comprising mixed oxides of Mn and Mg are well
suited for incorporation of dopants because magnesium atoms can be
easily substituted by other atoms as long as their size is
comparable with magnesium. A family of "doped" Mg.sub.6MnO.sub.8
compounds with the composition M.sub.(x)Mg.sub.(6-x)MnO.sub.8,
wherein each M is independently a dopant as defined herein and x is
0 to 6, can thus be created. The oxidation state of Mn can be tuned
by selecting different amounts (i.e., different values of x) of M
with different oxidation states, for example
Li.sub.(x)Mg.sub.(6-x)MnO.sub.8 would contain a mixture of Mn(IV)
and Mn(V) with x<1 and a mixture that may include Mn(V), Mn(VI),
Mn(VII) with x>1. The maximum value of x depends on the ability
of a particular atom M to be incorporated in the Mg.sub.6MnO.sub.8
crystal structure and therefore varies depending on M. It is
believed that the ability to tune the manganese oxidation state as
described above could have advantageous effect on the catalytic
activity of the disclosed nanowires.
[0315] Examples of nanowires comprising Li/Mn/Mg/B and an
additional dopant include; Li/Mn/Mg/B doped with Co; Li/Mn/Mg/B
doped with Na, Li/Mn/Mg/B doped with Be; Li/Mn/Mg/B doped with Al;
Li/Mn/Mg/B doped with Hf; Li/Mn/Mg/B doped with Zr; Li/Mn/Mg/B
doped with Zn; Li/Mn/Mg/B doped with Rh and Li/Mn/Mg/B doped with
Ga. Nanowires comprising Li/Mn/Mg/B doped with different
combinations of these dopants are also provided. For example, in
some embodiments the Li/Mn/Mg/B nanowires are doped with Na and Co.
In other embodiments, the Li/Mn/Mg/B nanowires are doped with Ga
and Na.
[0316] In other embodiments, nanowires comprising Mn/W with or
without dopants are provided. For example, the present inventors
have found through high throughput testing that nanowires
comprising Mn/W and various dopants are good catalysts in the OCM
reaction. Accordingly, in some embodiments, the Mn/W nanowires are
doped with Ba. In other embodiments, the Mn/W nanowires are doped
with Be. In yet other embodiments, the Mn/W nanowires are doped
with Te.
[0317] In any of the above embodiments, the Mn/W nanowires may
comprise a SiO.sub.2 support. Alternatively, the use of different
supports such as ZrO.sub.2, HfO.sub.2 and In.sub.2O.sub.3 in any of
the above embodiments has been shown to promote OCM activity at
reduced temperature compared to the same catalyst supported on
silica with limited reduction in selectivity.
[0318] Nanowires comprising rare earth oxides doped with various
elements are also effective catalysts in the OCM reaction. In
certain specific embodiments, the rare earth oxide or oxy-hydroxide
can be any rare earth, preferably La, Nd, Eu, Sm, Yb, Gd. In
certain embodiments of the nanowires comprising rare earth elements
or yttria, the dopant comprises alkali earth (group 2) elements.
The degree of effectiveness of a particular dopant is a function of
the rare earth used and the concentration of the alkali earth
dopant. In addition to Alkali earth elements, further embodiments
of the rare earth or yttria nanowires include embodiments wherein
the nanowires comprise alkali elements as dopants, which further
promote the selectivity of the OCM catalytic activity of the doped
material. In yet other embodiments of the foregoing, the nanowires
comprise both an alkali element and alkali earth element as dopant.
In still further embodiments, an additional dopant can be selected
from an additional rare earth and groups 3, 4, 8, 9, 10, 13,
14.
[0319] The foregoing rare earth catalyst may be doped prior to, or
after formation of the rare earth oxide. In one embodiment, the
corresponding rare earth salt is mixed with the corresponding
dopant salt to form a solution or a slurry which is dried and then
calcined in a range of 400.degree. C. to 900.degree. C., or between
500.degree. C. and 700.degree. C. In another embodiment, the rare
earth oxide is formed first through calcination of a rare earth
salt and then contacted with a solution comprising the doping
element prior to drying and calcination between 300.degree. C. and
800.degree. C., or between 400.degree. C. and 700.degree. C.
[0320] In other embodiments, the nanowires comprise La.sub.2O.sub.3
or LaO.sub.y(OH).sub.x, wherein y ranges from 0 to 1.5, x ranges
from 0 to 3 and 2y+x=3, doped with Na, Mg, Ca, Sr, Ga, Sc, Y, Zr,
In, Nd, Eu, Sm, Ce, Gd or combinations thereof. In yet further
embodiments, the La.sub.2O.sub.3 or LaO.sub.y(OH).sub.x nanowires
are doped with binary dopant combinations, for example Eu/Na;
Eu/Gd; Ca/Na; Eu/Sm; Eu/Sr; Mg/Sr; Ce/Mg; Gd/Sm, Mg/Na, Mg/Y,
Ga/Sr, Nd/Mg, Gd/Na or Sm/Na. In some other embodiments, the
La.sub.2O.sub.3 or LaO.sub.y(OH).sub.x nanowires are doped with a
ternary dopant combination, for example Ca--Mg--Na.
[0321] In other embodiments, the nanowires comprise Nd.sub.2O.sub.3
or NdO.sub.y(OH).sub.x, wherein y ranges from 0 to 1.5, x ranges
from 0 to 3 and 2y+x=3, doped with Sr, Ca, Rb, Li, Na or
combinations thereof. In certain other embodiments, the
Nd.sub.2O.sub.3 or NdO.sub.y(OH).sub.x nanowires are doped with
binary dopant combinations, for example Ca/Sr, Rb/Sr, Ta/Sr or
Al/Sr.
[0322] In still other examples of doped nanowires, the nanowires
comprise Yb.sub.2O.sub.3 or YbO.sub.y(OH).sub.x, wherein y ranges
from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, doped with Sr, Ca,
Ba, Nd or combinations thereof. In certain other embodiments, the
Yb.sub.2O.sub.3 or YbO.sub.y(OH).sub.x OCM nanowires are doped with
a binary combination, for example of Sr/Nd.
[0323] Still other examples of doped nanowires Eu.sub.2O.sub.3 or
EuO.sub.y(OH).sub.x nanowires, wherein y ranges from 0 to 1.5, x
ranges from 0 to 3 and 2y+x=3, doped with Sr, Ba, Sm, Gd, Na or
combinations thereof or a binary dopant combination, for example
Sr/Na or Sm/Na.
[0324] Example of dopants for Sm.sub.2O.sub.3 or
SmO.sub.y(OH).sub.x nanowires, wherein x and y are each
independently an integer from 1 to 10, include Sr, and examples of
dopants for Y.sub.2O.sub.3 or YO.sub.y(OH).sub.x nanowires, wherein
y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, comprise
Ga, La, Nd or combinations thereof. In certain other embodiments,
the Y.sub.2O.sub.3 or YO.sub.y(OH).sub.x nanowires comprise a
binary dopant combination, for example Sr/Nd, Eu/Y or Mg/Nd or a
tertiary dopant combination, for example Mg/Nd/Fe.
[0325] In yet other embodiments, the nanowires comprise
Ln.sub.2O.sub.3 or Ln.sub.zO.sub.y(OH).sub.x, wherein Ln is at each
occurrence, independently a lanthanide, x ranges from 0 to 3 and
2y+x=3, y ranges from 0 to 1.5, and z is 1, 2 or 3, and the
nanowires are doped with Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf,
V, Nb, Ta, Mo, W, Mn, Ni, Pd, Pt, Cu, Ag, Au, Zn, Al, Ga, In, Tl,
Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te or combinations thereof. In
certain other embodiments, the Ln.sub.2O.sub.3 or
Ln.sub.zO.sub.y(OH).sub.x nanowires comprise only one dopant, for
example Sr, a binary dopant combination, for example Na/Mg, Na/Sr,
Mg/Sr, Li/Cs, Sr/W, Hf/Bi, Na/Eu, Zn/K, Sb/Ag, Sr/Ta, a tertiary
dopant combination, for example Li/Na/Sr, Na/La/Eu, Li/Sr/Cs,
Dy/Rb/Gd, Mg/La/K, or a quaternary dopant combination, for example
Na/Zr/Eu/Ca, Na/La/Eu/In, Na/K/Mg/Tm, Li/Cs/Sr/Tm, Ba/Tm/Zn/K,
Mg/La/Yb/Zn.
[0326] Rare earth nanowires, which without doping often have low
OCM selectivity, can be greatly improved by doping to reduce their
combustion activity. In particular, nanowires comprising CeO.sub.2
and Pr.sub.2O.sub.3 tend to have strong total oxidation activity
for methane, however doping with additional rare earth elements can
significantly moderate the combustion activity and improve the
overall utility of the catalyst. Example of dopants for improving
the selectivity for Pr.sub.2O.sub.3 or PrO.sub.y(OH).sub.x
nanowires, wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and
2y+x=3, comprise binary dopants, for example Nd/Mg, La/Mg or
Yb/Sr.
[0327] In some embodiments, dopants are present in the nanowires
in, for example, less than 50 at %, less than 25 at %, less than 10
at %, less than 5 at % or less than 1 at %.
[0328] In other embodiments of the nanowires, the atomic ratio
(w/w) of the one or more metal elements selected from Groups 1-7
and lanthanides and actinides in the form of an oxide and the
dopant ranges from 1:1 to 10,000:1, 1:1 to 1,000:1 or 1:1 to
500:1.
[0329] In further embodiments, the nanowires comprise one or more
metal elements from Group 2 in the form of an oxide and a dopant
from Group 1. In further embodiments, the nanowires comprise
magnesium and lithium. In other embodiments, the nanowires comprise
one or more metal elements from Group 2 and a dopant from Group 2,
for example, in some embodiments, the nanowires comprise magnesium
oxide and barium. In other embodiments, the nanowires comprise one
or more metal elements from Group 2, a dopant from Group 2 and an
additional dopant, for example, in some embodiments, the nanowires
comprise magnesium oxide and are doped with strontium and tungsten
dopants (i.e., Sr/W/MgO). In another embodiment, the nanowires
comprise an element from the lanthanides in the form of an oxide
and a dopant from Group 1 or Group 2. In further embodiments, the
nanowires comprise lanthanum and strontium.
[0330] Various methods for preparing doped nanowires are provided.
In one embodiment, the doped nanowires can be prepared by
co-precipitating a nanowire metal oxide precursor and a dopant
precursor. In these embodiments, the doping element may be directly
incorporated into the nanowire.
Template Directed Synthesis of Nanowires
[0331] In some embodiments, the nanowires can be prepared in a
solution phase using an appropriate template. In this context, an
appropriate template can be any synthetic or natural material, or
combination thereof, that provides nucleation sites for binding
ions (e.g. metal element ions and/or hydroxide or other anions) and
causing the growth of a nanowire. The templates can be selected
such that certain control of the nucleation sites, in terms of
their composition, quantity and location can be achieved in a
statistically significant manner. The templates are typically
linear or anisotropic in shape, thus directing the growth of a
nanowire.
[0332] In contrast to other template directed preparation of
nanostructures, the nanowires of the invention are generally not
prepared from nanoparticles deposited on a template in a reduced
state which are then heat treated and fused into an elongated
nanoporous nanostructure. In particular, such methods are not
generally applicable to continuous nanowires comprising one or more
elements from any of Groups 1 through 7, lanthanides, actinides or
combinations thereof. Instead of forming a plurality of catalyst
nanoparticles, nanocrystals, or nanocrystallites on the surface of
the template, the nanowires of the invention are preferably
prepared by nucleation of an oxidized metal element (e.g., in the
form of a metal ion) and subsequent growth of a nanowire. After
nucleation of the oxidized metal element, the nanowires are
generally calcined to produce the desired oxide, but annealing of
nanoparticles is not necessary to form the nanowires.
[0333] Accordingly, the nanowires used in the context of the
invention have a number of properties that differentiate them from
other nanostructures, such as those created as fused aggregates of
nanoparticles. In particular, the nanowires are characterized as
having one or more of; a substantially non-nanoporous structure, an
average crystal domain size, either before and/or after
calcination, of greater than 5 nm, and an anisotropic crystal
habit.
[0334] In the context of non-nanoporous nanowires, preferred
compositions are distinguished from elongated nanostructures formed
as nanoporous aggregates of nanoparticles by virtue of their
substantially non-nanoporous structures. Such substantially
non-nanoporous nanowire structures will preferably have a surface
area of less than 150 m.sup.2/g, more preferably less than 100
m.sup.2/g, less than 50 m.sup.2/g, less than 40 m.sup.2/g, less
than 30 m.sup.2/g less than 25 m.sup.2/g, less than 20 m.sup.2/g,
less than 15 m.sup.2/g, less than 10 m.sup.2/g, or between 1
m.sup.2/g and any of the foregoing. As will be appreciated,
nanowires created through templating processes, where additional
aggregates may fuse to a non-nanoporous or substantially
non-nanoporous nanowire core, will typically have higher surface
areas, e.g., surface areas toward the higher end of the range,
while nanowires created from other processes, e.g., by hydrothermal
processes, will typically have lower surface areas.
[0335] In certain aspects, the nanowires of the invention are
characterized by relatively large crystal domain sizes in the
context of relatively high surface area nanowire structures. In
particular, and as noted previously, for those nanowires of the
invention having an average crystal domain size in at least one
crystal dimension that is greater than 5 nm, preferred nanowires of
the invention will typically have an average crystal domain size in
at least one crystal dimension that is greater than 10 nm, and in
more preferred aspects, greater than 20 nm.
[0336] In certain embodiments, the nanowires of the invention may
also be characterized by additional structural properties. For
example, in certain aspects, the nanowires of the invention may be
characterized by a continuous crystal structure within the
nanowire, excluding stacking faults. In certain aspects, the
nanowires of the invention may be characterized by an aligned
crystal structure within the nanowire consisting of parallel,
aligned crystal domains.
[0337] In some embodiments, methods for forming nanowires having
the empirical formula M4.sub.wM5.sub.xM6.sub.yO.sub.z are provided,
wherein M4 comprises one or more elements selected from Groups 1
through 4, M5 comprises one or more elements selected from Group 7
and M6 comprises one or more elements selected from Groups 5
through 8 and Groups 14 through 15 and w, x, y and z are integers
such that the overall charge is balanced. The methods comprise
combining one or more sources of M4, one or more sources of M5, and
one or more sources of M6 in the presence of a templating agent and
a solvent to form a mixture. In certain embodiments the templating
agent is a polymer, for example PVP (polyvinlpyrrolidone), PVA
(polyvinylalcohol), PEI (polyethyleneimine), PEG
(polyethyleneglycol), polyether, polyesters, polyamides, dextran
and other sugar polymers, functionalized hydrocarbon polymers,
functionalized polystyrene, polylactic acid, polycaprolactone,
polyglycolic acid, poly(ethylene glycol)-poly(propylene
glycol)-poly(ethylene glycol), copolymers or combinations
thereof.
[0338] In certain embodiments, M4 includes one or more elements
selected from Group 1, such as Na, while M6 includes one or more
elements selected from Group 6, such as W and M3 is Mn. In one
embodiment, M4 is Na and the source of M4 is NaCl, M5 is Mn and the
source of M5 is Mn(NO.sub.3).sub.2, M6 is W and the source of M6 is
WO.sub.3, the solvent is water, and the templating agent is a
polymer, for example PVP (polyvinlpyrrolidone), PVA
(polyvinylalcohol), PEI (polyethyleneimine), PEG
(polyethyleneglycol), polyether, polyesters, polyamides, dextran
and other sugar polymers, functionalized hydrocarbon polymers,
functionalized polystyrene, polylactic acid, polycaprolactone,
polyglycolic acid, poly(ethylene glycol)-poly(propylene
glycol)-poly(ethylene glycol), copolymers or combinations
thereof.
[0339] In various embodiments, the source of M4 can be one or more
of a chloride, bromide, iodide, oxychloride, oxybromide, oxyiodide,
nitrate, oxynitrate, sulfate or phosphate salt of any of Group 1,
Group 2, Group 3, or a Group 4 element. In an embodiment, sources
of M4 include LiCl, KCl, MgCl.sub.2, CaCl.sub.2, ScCl.sub.3,
TiCl.sub.4, KBr, CaBr.sub.2, Sc(NO.sub.3).sub.3, Y(NO.sub.3).sub.3,
TiBr.sub.4, ZrBr.sub.4, Zr(NO.sub.3).sub.4, ZrOCl.sub.2,
ZrO(NO.sub.3).sub.2, Na.sub.2SO.sub.4, and Zr(SO.sub.4).sub.2. For
any given source of M4, a source of M6 can be one or more of an
oxide, oxide salt, or an oxyacid of any of Group 5, Group 6, Group
7, Group 8, Group 14 and Group 15 elements. In an embodiment,
sources of M6 include MoO.sub.3, (NH.sub.4).sub.6MO.sub.7O.sub.24,
WO.sub.3, Na.sub.2WO.sub.4, H.sub.2WO.sub.4, Co.sub.2O.sub.3,
P.sub.2O.sub.5, H.sub.3PO.sub.4 and H.sub.2SiO.sub.4. For any given
combination of a source of M4 and a source of M6, a source of Mn
can be, but is not limited to, any chloride, bromide, nitrate, or
sulfate of manganese, including MnCl.sub.2, MnCl.sub.3, MnCl.sub.4,
Mn(NO.sub.3).sub.3, MnSO.sub.4 and Mn.sub.2(SO.sub.4).sub.3.
[0340] In still other embodiments, the templating agent can include
a surfactant, such as tetraoctylammonium chloride, ammonium lauryl
sulfate, or lauryl glucoside. For any templating agent or any
source of M4, M6, or Mn, the solvent can include an organic
solvent, such as ethanol, diethyl ether, or acetonitrile.
Additionally, any embodiment of the method for forming a nanowire
described above can include any additional component in the
reaction mixture, such as a base.
[0341] Nanowire-forming methods of various embodiments of the
invention comprise combining a source of M4, a source of M5, a
source of M6, a templating agent (e.g., polymer), and a solvent in
a reaction mixture. In other embodiments, however, nanowire-forming
methods of the present invention comprise combining two of a source
of M4, a source of M5 and a source of M6 in the presence of a
templating agent and a solvent to form an intermediate nanowire and
then combining a remainder of the source of M4, the source of M5
and the source of M6 with the intermediate nanowire, wherein M4
includes one or more elements selected from Group 1, Group 2, Group
3 and Group 4 elements, wherein M5 includes one or more elements
selected from Group 7, and wherein M6 includes one or more elements
selected from Group 5, Group 6, Group 7, Group 8, Group 14 and
Group 15 elements. In an embodiment, an intermediate nanowire is
formed by combining the source of M5 and the source of M6 in the
presence of the templating agent and the solvent, followed by
combining the intermediate nanowire with the source of M4.
[0342] 1. Polymer Template
[0343] As discussed above, the present disclosure provides
nanowires and methods for preparing the same via polymer template
methods. Polymer or "soft" templates have extensively been used in
materials synthesis to prepare materials with unique nano and
microstructures. Polymer templated materials may have irregular,
ordered, or shape specific structures. To a large extent, the
resulting structure is predicated on the interaction of the polymer
and the inorganic material to be templated. For example, changing
the polymer templating agent while leaving the metal precursor the
same can have drastic effects on the metal/metal oxide end
structure. The ability to tune the metal/metal oxide structure to
achieve a desired catalytic performance has been an ongoing goal in
the field of catalysis. Thus, the presently disclosed methods find
utility in for preparation of carious catalytic structures, for
example nanowires.
[0344] Polymers can be used to prepare templated and textured metal
oxide OCM catalysts, for example in the form of nanowires. This
invention describes a simple method to prepare metal and mixed
metal oxide OCM catalysts using polymer templates. In one
embodiment, the disclosed methods employ polymers (e.g.,
water-soluble polymers) with a wide range of molecular weights, as
the templating source. Exemplary polymers include PVP
(polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyether,
polyesters, polyamides, dextran and other sugar polymers,
functionalized hydrocarbon polymers, functionalized polystyrene,
polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol) and copolymers
and combinations thereof. In some embodiments, the polymer template
is functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol, halogen or thiol groups. For example the polymer
template may be a hydrocarbon or polystyrene polymer functionalized
with at least one of amine, carboxylic acid, sulfate, alcohol
halaogen or thiol groups.
[0345] Briefly, a metal precursor and polymer are dissolved in
water to produce a viscous solution. The solution is dried and
calcined (oven or microwave) to remove the polymer template. In
some embodiments, multiple metal (e.g., M1, M2, etc.) precursors
are dissolved in a polymer solution. The solution is dried and
calcined as described above to yield mixed metal oxide systems for
OCM catalysis. Another embodiment uses freeze drying to dry the
polymer/metal solution to prepare a more controllable porosity in
the metal and mixed metal oxide materials.
[0346] Some embodiments comprise use of polymers that readily form
gels to prepare metal oxides and mixed metal oxides for OCM
catalysts. For example, agarose readily forms a gel that can be
used as a templating source by impregnating the gel with metal
precursors. One embodiment of the present disclosure comprises
impregnating a gel (e.g., agarose) with one or more metal
precursors to prepare a nanowire comprising one or more metals, for
example a metal oxide or mixed metal oxide. The gel may be
impregnated with multiple metals in one step or via a step wise
impregnation.
[0347] In another embodiment, the disclosed methods comprise
treating a metal-polymer gel composite (e.g., agarose) with a base
to precipitate the metal precursors within the gel framework. The
precipitated metals may then optionally be calcined. Another
embodiment uses freeze drying to remove the water from the
metal-polymer gel composite. The agarose is removed by oven or
microwave calcination to yield metal and mixed metal OCM
catalysts.
[0348] The "Pechini" Method is a convenient method to prepare
evenly dispersed mixed metal oxides. The general procedure
comprises use of a multifunctional coordinating ligand that
chelates to the metal in solution to create a metal coordination
complex that can be polymerized in-situ, using a polyalcohol, to
prepare a metal/organic composite. Normally an
alpha-hydroxycarboxylic acid, such as citric acid, is used to form
a stable metal complex and can be esterified/cross-linked with a
poly-hydroxyalcohol, such as ethylene glycol or glycerol, to form a
polymeric resin. Immobilization of the metal complexes in the resin
reduces metal segregation and facilitates compositional
homogeneity.
[0349] 2. Nucleation
[0350] Nucleation is the process of forming an inorganic nanowire
in situ by converting soluble precursors (e.g., metal salts and
anions) into nanocrystals in the presence of a template (e.g., a
polymer template). Typically, the nucleation and growth takes place
from multiple binding sites along the length of the polymer
template in parallel. The growth continues until a structure
encasing the polymer template is formed. In some embodiments this
structure is single-crystalline. In other embodiments the structure
is amorphous, and in other embodiments the structure is
polycrystalline. If desired, upon completion of the synthesis the
polymer template can be removed by thermal treatment
(.about.300.degree. C.) in air or oxygen, without significantly
affecting either the structure or shape of the inorganic material.
In addition, dopants can be either simultaneously incorporated
during the growth process or, in another embodiment, dopants can be
incorporated via impregnation techniques.
[0351] (a) Nanowire Growth Methods
[0352] FIG. 6 shows a flow chart of a nucleation process for
forming a nanowire comprising a metal oxide. A polymer solution is
first prepared (block 504), to which metal salt precursor
comprising metal ions is added (block 510). Thereafter, an anion
precursor is added (block 520). It is noted that, in various
embodiments, the additions of the metal ions and anion precursor
can be simultaneous or sequentially in any order. Under appropriate
conditions (e.g., pH, molar ratio of the polymer and metal salt,
molar ratio of the metal ions and anions, addition rate, etc.), the
metal ions and anions become bound to the polymer, nucleate and
grow into a nanowire of M.sub.mX.sub.nZ.sub.p composition (block
524). Following calcinations, nanowires comprising M.sub.mX.sub.n
are transformed to nanowires comprising metal oxide
(M.sub.xO.sub.y) (block 530). An optional step of doping (block
534) incorporates a dopant (D.sup.p+) in the nanowires comprising
metal oxide (M.sub.xO.sub.y, wherein x and y are each independently
a number from 1 to 100. For ease of illustration, FIG. 6 depicts
calcinations prior to doping; however, in certain embodiments
doping may be performed prior to calcinations.
[0353] Thus, one embodiment provides a method for preparing a
nanowire comprising a metal oxide, a metal oxy-hydroxide, a metal
oxycarbonate or a metal carbonate, the method comprising:
[0354] a) providing a solution comprising a plurality of polymer
templates;
[0355] (b) introducing at least one metal ion and at least one
anion to the solution under conditions and for a time sufficient to
allow for nucleation and growth of a nanowire comprising a
plurality of metal salts (M.sub.mX.sub.nZ.sub.p) on the template;
and
[0356] (c) converting the nanowire (M.sub.mX.sub.nZ.sub.p) to a
metal oxide nanowire comprising a plurality of metal oxides
(M.sub.xO.sub.y), metal oxy-hydroxides (M.sub.xO.sub.YOH.sub.z),
metal oxycarbonates (M.sub.xO.sub.y(CO.sub.3).sub.z), metal
carbonate (M.sub.x(CO.sub.3).sub.y) or combinations thereof
[0357] wherein:
[0358] M is, at each occurrence, independently a metal element from
any of Groups 1 through 7, lanthanides or actinides;
[0359] X is, at each occurrence, independently hydroxide,
carbonate, bicarbonate, phosphate, hydrogenphosphate,
dihydrogenphosphate, sulfate, nitrate or oxalate;
[0360] Z is O;
[0361] n, m, x and y are each independently a number from 1 to 100;
and
[0362] p is a number from 0 to 100.
[0363] In some embodiments of the foregoing, the polymer template
comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyether,
polyesters, polyamides, dextran and other sugar polymers,
functionalized hydrocarbon polymers, functionalized polystyrene,
polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol), copolymers or
combinations thereof. In some embodiments, the polymer template is
functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol, halogen or thiol groups. For example the polymer
template may be a hydrocarbon or polystyrene polymer functionalized
with at least one of amine, carboxylic acid, sulfate, alcohol,
halogen or thiol groups.
[0364] In some embodiments, the nanowire is dried in an oven, while
in other embodiments the nanowire is freeze dried or air dried. The
drying method may have an effect on the final morphology, pore
size, etc. of the resulting nanowire. Additionally, the solution
comprising the polymer template may be in the form of a gel and the
at least one metal ion is impregnated therein. The gel may then be
dried as described above. In some embodiments, the metal
impregnated gel is treated with a base to precipitate the metal. In
some different embodiments, the polymer template is removed from
the nanowire by heat treatment or other removal means.
[0365] In certain other variations of the foregoing, two or more
different metal ions may be used. This produces nanowires
comprising a mixture of two or more metal oxides. Such nanowires
may be advantageous in certain catalytic reactions. For example, in
some embodiments the nanowire catalysts may comprise at least a
first and second metal oxide wherein the first metal oxide has
better OCM activity than the second metal oxide and the second
metal oxide has better ODH activity than the first metal oxide. In
certain embodiments of the above, Applicants have found that it may
be advantageous to perform multiple sequential additions of the
metal ion, This addition technique may be particularly applicable
to embodiments wherein two or more different metal ions are
employed to form a mixed nanowire (M1M2X.sub.xY.sub.y, wherein M1
and M2 are different metal elements), which can be converted to
M1M2O.sub.z, for example by calcination. The slow addition may be
performed over any period of time, for example from 1 day to 1
week. In this regard, use of a syringe pump or an automatic (e.g.,
robotic) liquid dispenser may be advantageous. Slow addition of the
components help ensure that they will nucleate on the polymer
template instead of non-selectively precipitate.
[0366] In various embodiments, the polymer templates are selected
from PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyether,
polyesters, polyamides, dextran and other sugar polymers,
functionalized hydrocarbon polymers, functionalized polystyrene,
polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol), copolymers or
combinations thereof. In some embodiments, the polymer template is
functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol, halogen or thiol groups. For example the polymer
template may be a hydrocarbon or polystyrene polymer functionalized
with at least one of amine, carboxylic acid, sulfate, alcohol,
halogen or thiol groups.
[0367] In further embodiments, the metal ion is provided by adding
one or more metal salt (as described herein) to the solution. In
other embodiments, the anion is provided by adding one or more
anion precursor to the solution. In various embodiments, the metal
ion and the anion can be introduced to the solution simultaneously
or sequentially in any order. In some embodiments, the nanowire
(M.sub.mX.sub.nZ.sub.p) is converted to a metal oxide nanowire by
calcination, which is a thermal treatment that transforms or
decomposes the M.sub.mX.sub.nZ.sub.p nanowire to a metal oxide. In
yet another embodiment, the method further comprises doping the
metal oxide nanowire with a dopant. Doping may be performed either
before or after calcination. Converting the nanowire to a metal
oxide (or oxy-hydroxide, oxy-carbonate, or carbonate, etc.)
generally comprises calcining.
[0368] In a variation of the above method, mixed metal oxides can
be prepared (as opposed to a mixture of metal oxides). Mixed metal
oxides can be represented by the following formula
M1.sub.wM2.sub.xM3.sub.yO.sub.z, wherein M1, M2 and M3 are each
independently absent or a metal element, and w, x, y and z are
integers such that the overall charge is balanced. Mixed metal
oxides comprising more than three metals are also contemplated and
can be prepared via an analogous method. Such mixed metal oxides
find utility in a variety of the catalytic reactions disclosed
herein. One exemplary mixed metal oxide is
Na.sub.10MnW.sub.5O.sub.17.
[0369] Thus, one embodiment provides a method for preparing a mixed
metal oxide nanowire comprising a plurality of mixed metal oxides
(M1.sub.wM2.sub.xM3.sub.yO.sub.z), the method comprising:
[0370] a) providing a solution comprising a plurality of polymer
templates;
[0371] (b) introducing metal salts comprising M1, M2 and M3 to the
solution under conditions and for a time sufficient to allow for
nucleation and growth of a nanowire comprising a plurality of the
metal salts on the template; and
[0372] (c) converting the nanowire to a mixed metal oxide nanowire
comprising a plurality of mixed metal oxides
(M1.sub.wM2.sub.xM3.sub.yO.sub.z),
[0373] wherein:
[0374] M1, M2 and M3 are, at each occurrence, independently a metal
element from any of Groups 1 through 7, lanthanides or
actinides;
[0375] n, m, x and y are each independently a number from 1 to 100;
and
[0376] p is a number from 0 to 100.
[0377] In some embodiments of the foregoing, the polymer template
comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyether,
polyesters, polyamides, dextran and other sugar polymers,
functionalized hydrocarbon polymers, functionalized polystyrene,
polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol), copolymers or
combinations thereof. In some embodiments, the polymer template is
functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol, halogen or thiol groups. For example the polymer
template may be a hydrocarbon or polystyrene polymer functionalized
with at least one of amine, carboxylic acid, sulfate, alcohol or
thiol groups.
[0378] In some embodiments, the nanowire is dried in an oven, while
in other embodiments the nanowire is freeze dried or air dried. The
drying method may have an effect on the final morphology, pore
size, etc. of the resulting nanowire. Additionally, the solution
comprising the polymer template may be in the form of a gel and the
at least one metal salts are impregnated therein. The gel may then
be dried as described above. In some embodiments, the metal
impregnated gel is treated with a base to precipitate the metal. In
some different embodiments, the polymer template is removed from
the nanowire by heat treatment or other removal means.
[0379] In other embodiments, the present disclosure provides a
method for preparing metal oxide nanowires which may not require a
calcination step. Thus, in some embodiments the method for
preparing metal oxide nanowires comprises:
[0380] (a) providing a solution that includes a plurality of
polymer templates; and
[0381] (b) introducing a compound comprising a metal to the
solution under conditions and for a time sufficient to allow for
nucleation and growth of a nanowire (M.sub.mY.sub.n) on the
template;
[0382] wherein:
[0383] M is a metal element from any of Groups 1 through 7,
lanthanides or actinides;
[0384] Y is O;
[0385] n and m are each independently a number from 1 to 100.
[0386] In some embodiments of the foregoing, the polymer template
comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI
(polyethyleneimine), PEG (polyethyleneglycol), polyether,
polyesters, polyamides, dextran and other sugar polymers,
functionalized hydrocarbon polymers, functionalized polystyrene,
polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol), copolymers or
combinations thereof. In some embodiments, the polymer template is
functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol, halogen or thiol groups. For example the polymer
template may be a hydrocarbon or polystyrene polymer functionalized
with at least one of amine, carboxylic acid, sulfate, alcohol,
halogen or thiol groups.
[0387] In some embodiments, the nanowire is dried in an oven, while
in other embodiments the nanowire is freeze dried or air dried. The
drying method may have an effect on the final morphology, pore
size, etc. of the resulting nanowire. Additionally, the solution
comprising the polymer template may be in the form of a gel and the
at least one metal is impregnated therein. The gel may then be
dried as described above. In some embodiments, the metal
impregnated gel is treated with a base to precipitate the metal. In
some different embodiments, the polymer template is removed from
the nanowire by heat treatment or other removal means.
[0388] In some specific embodiments of the foregoing method, M is
an early transition metal, for example V, Nb, Ta, Ti, Zr, Hf, W, Mo
or Cr. In other embodiments, the metal oxide is WO.sub.3. In yet
another embodiment, the method further comprises doping the metal
oxide nanowire with a dopant. In some further embodiments, a
reagent is added which converts the compound comprising a metal
into a metal oxide.
[0389] In another embodiment the disclosure provides a method for
preparing a nanowire comprising a metal oxide, a metal
oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the
method comprises:
[0390] a) providing a solution comprising a plurality of a
multifunctional coordinating ligand;
[0391] (b) introducing at least one metal ion to the solution,
thereby forming a metal ion-ligand complex;
[0392] (c) introducing a polyalcohol to the solution, wherein the
polyalcohol polymerizes with the metal-ion ligand complex to form a
polymerized metal ion-ligand complex.
[0393] In some embodiments, the multifunctional coordinating ligand
is an alpha-hydroxycarboxylic acid, for example citric acid. In
other embodiments, the polyalcohol is ethylene glycol or glycerol.
In yet other embodiments, the method further comprises heating the
polymerized metal ion-ligand complex to remove substantially all
organic material, and optionally heating the remaining inorganic
metal to convert it to a metal oxide (i.e., calcine). In another
embodiment, nanowires are prepared by using metal salts sensitive
to water hydrolysis, for example NbCl.sub.5, WCl.sub.6, TiCl.sub.4,
ZrCl.sub.4. A polymer template can be placed in ethanol along with
the metal salt. Water is then slowly added to the reaction in order
to convert the metals salts to metal oxide coated template.
[0394] By varying the nucleation conditions, including (without
limitation): incubation time of polymer and metal salt; incubation
time of polymer and anion; concentration of polymer; metal ion
concentration, anion concentration, sequence of adding anion and
metal ions; pH; polymer composition; polymer size; solution
temperature in the incubation step and/or growth step; types of
metal precursor salt; types of anion precursor; addition rate;
number of additions; amount of metal salt and/or anion precursor
per addition, the time that lapses between the additions of the
metal salt and anion precursor, including, e.g., simultaneous (zero
lapse) or sequential additions followed by respective incubation
times for the metal salt and the anion precursor, stable nanowires
of diverse compositions and surface properties can be prepared. For
example, in certain embodiments the pH of the nucleation conditions
is at least 7.0, at least 8.0, at least 9.0, at least 10.0, at
least 11.0, at least 12.0 or at least 13.0.
[0395] As noted above, the rate of addition of reactants (e.g.,
metal salt, metal oxide, anion precursor, etc.) is one parameter
that can be controlled and varied to produce nanowires having
different properties. During the addition of reactants to a
solution containing an existing nanowire and/or a templating
material, a critical concentration is reached for which the speed
of deposition of solids on the existing nanowire and/or templating
material matches the rate of addition of reactants to the reaction
mixture. At this point, the concentration of soluble cation
stabilizes and stops rising. Thus, nanowire growth can be
controlled and maximized by maintaining the speed of addition of
reactants such that near super-saturation concentration of the
cation is maintained. This helps ensure that no undesirable
nucleation occurs. If super-saturation of the anion (e.g.,
hydroxide) is exceeded, a new solid phase can start nucleating
which allows for non-selective solid precipitation, rather than
nanowire growth. Thus, in order to selectively deposit an inorganic
layer on an existing nanowire and/or a templating material, the
addition rate of reactants should be controlled to avoid reaching
super-saturation of the solution containing the suspended
solids.
[0396] Accordingly, in one embodiment, reactant is repeatedly added
in small doses to slowly build up the concentration of the reactant
in the solution containing the template. In some embodiments, the
speed of addition of reactant is such that the reactant
concentration in the solution containing the template is near (but
less than) the saturation point of the reactant. In some other
embodiments, the reactant is added portion wise (i.e., step
addition) rather than continuously. In these embodiments, the
amount of reactant in each portion, and the time between addition
of each portion, is controlled such that the reactant concentration
in the solution containing the template is near (but less than) the
saturation point of the reactant. In certain embodiments of the
foregoing, the reactant is a metal cation while in other
embodiments the reactant is an anion.
[0397] Initial formation of nuclei on a template can be obtained by
the same method described above, wherein the concentration of
reactant is increased until near, but not above, the
supersaturation point of the reactant. Such an addition method
facilitates nucleation of the solid phase on the template, rather
than homogeneous non-seeding nucleation. In some embodiments, it is
desirable to use a slower reactant addition speed during the
initial nucleation phase as the super-saturation depression due to
the template might be quite small at this point. Once the first
layer of solid (i.e., nanowire) is formed on the template, the
addition speed can be increased.
[0398] In some embodiments, the addition rate of reactant is
controlled such that the precipitation rate matches the addition
rate of the reactant. In these embodiments, nanowires comprising
two or more different metals can be prepared by controlling the
addition rates of two or more different metal cation solutions such
that the concentration of each cation in the templating solution is
maintained at or near (but does not exceed) the saturation point
for each cation.
[0399] In some embodiments, the optimal speed of addition (and step
size if using step additions) is controlled as a function of
temperature. For example, in some embodiments the nanowire growth
rate is accelerated at higher temperatures. Thus, the addition rate
of reactants is adjusted according to the temperature of the
templating solution.
[0400] In other embodiments, modeling (iterative numeric rather
than algebraic) of the nanowire growth process is used to determine
optimal solution concentrations and supernatant re-cycling
strategies.
[0401] As noted above, the addition rate of reactants can be
controlled and modified to change the properties of the nanowires.
In some embodiments, the addition rate of a hydroxide source must
be controlled such that the pH of the templating solution is
maintained at the desired level. This method may require
specialized equipment, and depending on the addition rate, the
potential for localized spikes in pH upon addition of the hydroxide
source is possible. Thus, in an alternative embodiment the present
disclosure provides a method wherein the template solution
comprises a weak base that slowly generates hydroxide in-situ,
obviating the need for an automated addition sequence.
[0402] In the above embodiment, organic epoxides, such as but not
limited to propylene oxide and epichlorohydrin, are used to slowly
increase the template solution pH without the need for automated pH
control. The epoxides are proton scavengers and undergo an
irreversible ring-opening reaction with a nucleophilic anion of the
metal oxide precursor (such as but not limited to Cl.sup.- or
NO.sub.3.sup.-). The net effect is a slow homogenous raise in pH to
form metal hydroxy species in solution that deposit onto the
template surface. In some embodiments, the organic epoxide is
propylene oxide.
[0403] An attractive feature of this method is that the organic
epoxide can be added all at once, there is no requirement for
subsequent additions of organic epoxide to grow metal oxide
coatings over the course of the reaction. Due to the flexibility of
the "epoxide-assisted" coatings, it is anticipated that many
various embodiments can be employed to make new templated materials
(e.g., nanowires). For example, mixed metal oxide nanowires can be
prepared by starting with appropriate ratios of metal oxide
precursors and propylene oxide in the presence of polymer template.
In other embodiments, metal oxide deposition on the polymer
template can be done sequentially to prepare core/shell materials
(described in more detail below).
[0404] (b) Metal Salt
[0405] As noted above, the nanowires are prepared by nucleation of
metal ions in the presence of an appropriate template, for example,
a polymer. In this respect, any soluble metal salt may be used as
the precursor of metal ions that nucleate on the template. Soluble
metal salts of the metals from Groups 1 through 7, lanthanides and
actinides are particularly useful and all such salts are
contemplated.
[0406] In one embodiment, the soluble metal salt comprises
chlorides, bromides, iodides, nitrates, sulfates, acetates, oxides,
oxyhalides, oxynitrates, phosphates (including hydrogenphosphate
and dihydrogenphosphate) formates, alkoxides or oxalates of metal
elements from Groups 1 through 7, lanthanides, actinides or
combinations thereof. In more specific embodiments, the soluble
metal salt comprises chlorides, nitrates or sulfates of metal
elements from Groups 1 through 7, lanthanides, actinides or
combinations thereof. The present disclosure contemplates all
possible chloride, bromide, iodide, nitrate, sulfate, acetate,
oxide, oxyhalides, oxynitrates, phosphates (including
hydrogenphosphate and dihydrogenphosphate) formates, alkoxides and
oxalate salts of metal elements from Groups 1 through 7,
lanthanides, actinides or combinations thereof.
[0407] In another embodiment, the metal salt comprises LiCl, LiBr,
LiI, LiNO.sub.3, Li.sub.2SO.sub.4, LiCO.sub.2CH.sub.3,
Li.sub.2C.sub.2O.sub.4, Li.sub.3PO.sub.4, Li.sub.2HPO.sub.4,
LiH.sub.2PO.sub.4, LiCO.sub.2H, LiOR, NaCl, NaBr, NaI, NaNO.sub.3,
Na.sub.2SO.sub.4, NaCO.sub.2CH.sub.3, Na.sub.2C.sub.2O.sub.4,
Na.sub.3PO.sub.4, Na.sub.2HPO.sub.4, NaH.sub.2PO.sub.4,
NaCO.sub.2H, NaOR, KCl, KBr, KI, KNO.sub.3, K.sub.2SO.sub.4,
KCO.sub.2CH.sub.3, K.sub.2C.sub.2O.sub.4, K.sub.3PO4,
K.sub.2HPO.sub.4, KH.sub.2PO.sub.4, KCO.sub.2H, KOR, RbCl, RbBr,
RbI, RbNO.sub.3, Rb.sub.2SO.sub.4, RbCO.sub.2CH.sub.3,
Rb.sub.2C.sub.2O.sub.4, Rb.sub.3PO.sub.4, Rb.sub.2HPO.sub.4,
RbH.sub.2PO.sub.4, RbCO.sub.2H, RbOR, CsCl, CsBr, CsI, CsNO.sub.3,
Cs.sub.2SO.sub.4, CsCO.sub.2CH.sub.3, Cs.sub.2C.sub.2O.sub.4,
Cs.sub.3PO.sub.4, Cs.sub.2HPO.sub.4, CsH.sub.2PO.sub.4,
CsCO.sub.2H, CsOR, BeCl.sub.2, BeBr.sub.2, BeI.sub.2,
Be(NO.sub.3).sub.2, BeSO.sub.4, Be(CO.sub.2CH.sub.3).sub.2,
BeC.sub.2O.sub.4, Be.sub.3(PO4).sub.2, BeHPO.sub.4,
Be(H.sub.2PO.sub.4).sub.2, Be(CO.sub.2H).sub.2, Be(OR).sub.2,
MgCl.sub.2, MgBr.sub.2, MgI.sub.2, Mg(NO.sub.3).sub.2, MgSO.sub.4,
Mg(CO.sub.2CH.sub.3).sub.2, MgC.sub.2O.sub.4,
Mg.sub.3(PO.sub.4).sub.2, MgHPO.sub.4, Mg(H.sub.2PO.sub.4).sub.2,
Mg(CO.sub.2H).sub.2, Mg(OR).sub.2, CaCl.sub.2, CaBr.sub.2,
CaI.sub.2, Ca(NO.sub.3).sub.2, CaSO.sub.4,
Ca(CO.sub.2CH.sub.3).sub.2, CaC.sub.2O.sub.4,
Mg.sub.3(PO.sub.4).sub.2, MgHPO.sub.4, Mg(H.sub.2PO.sub.4).sub.2,
Mg(CO.sub.2H).sub.2, Mg(OR).sub.2, SrCl.sub.2, SrBr.sub.2,
SrI.sub.2, Sr(NO.sub.3).sub.2, SrSO.sub.4,
Sr(CO.sub.2CH.sub.3).sub.2, SrC.sub.2O.sub.4,
Sr.sub.3(PO.sub.4).sub.2, SrHPO.sub.4, Sr(H.sub.2PO.sub.4).sub.2,
Sr(CO.sub.2H).sub.2, Sr(OR).sub.2, BaCl.sub.2, BaBr.sub.2,
BaI.sub.2, Ba(NO.sub.3).sub.2, BaSO.sub.4,
Ba(CO.sub.2CH.sub.3).sub.2, BaC.sub.2O.sub.4,
Ba.sub.3(PO.sub.4).sub.2, BaHPO.sub.4, Ba(H.sub.2PO.sub.4).sub.2,
Ba(CO.sub.2H).sub.2, Ba(OR).sub.2, ScCl.sub.3, ScBr.sub.3,
ScI.sub.3, Sc(NO.sub.3).sub.3, Sc.sub.2(SO.sub.4).sub.3,
Sc(CO.sub.2CH.sub.3).sub.3, Sc.sub.2(C.sub.2O.sub.4).sub.3,
ScPO.sub.4, Sc.sub.2(HPO.sub.4).sub.3, Sc(H.sub.2PO.sub.4).sub.3,
Sc(CO.sub.2H).sub.3, Sc(OR).sub.3, YCl.sub.3, YBr.sub.3, YI.sub.3,
Y(NO.sub.3).sub.3, Y.sub.2(SO.sub.4).sub.3,
Y(CO.sub.2CH.sub.3).sub.3, Y.sub.2(C.sub.2O.sub.4).sub.3,
YPO.sub.4, Y.sub.2(HPO.sub.4).sub.3, Y(H.sub.2PO.sub.4).sub.3,
Y(CO.sub.2H).sub.3, Y(OR).sub.3, TiCl.sub.4, TiBr.sub.4, TiI.sub.4,
Ti(NO.sub.3).sub.4, Ti(SO.sub.4).sub.2, Ti(CO.sub.2CH.sub.3).sub.4,
Ti(C.sub.2O.sub.4).sub.2, Ti.sub.3(PO.sub.4).sub.4,
Ti(HPO.sub.4).sub.2, Ti(H.sub.2PO.sub.4).sub.4,
Ti(CO.sub.2H).sub.4, Ti(OR).sub.4, ZrCl.sub.4, ZrOCl.sub.2,
ZrBr.sub.4, ZrI.sub.4, Zr(NO.sub.3).sub.4, ZrO(NO.sub.3).sub.2,
Zr(SO.sub.4).sub.2, Zr(CO.sub.2CH.sub.3).sub.4,
Zr(C.sub.2O.sub.4).sub.2, Zr.sub.3(PO.sub.4).sub.4,
Zr(HPO.sub.4).sub.2, Zr(H.sub.2PO.sub.4).sub.4,
Zr(CO.sub.2H).sub.4, Zr(OR).sub.4, HfCl.sub.4, HfBr.sub.4,
HfI.sub.4, Hf(NO.sub.3).sub.4, Hf(SO.sub.4).sub.2,
Hf(CO.sub.2CH.sub.3).sub.4, Hf(C.sub.2O.sub.4).sub.2,
Hf.sub.3(PO.sub.4).sub.4, Hf(HPO.sub.4).sub.2,
Hf(H.sub.2PO.sub.4).sub.4, Hf(CO.sub.2H).sub.4, Hf(OR).sub.4,
LaCl.sub.3, LaBr.sub.3, LaI.sub.3, La(NO.sub.3).sub.3,
La.sub.2(SO.sub.4).sub.3, La(CO.sub.2CH.sub.3).sub.3,
La.sub.2(C.sub.2O.sub.4).sub.3, LaPO.sub.4,
La.sub.2(HPO.sub.4).sub.3, La(H.sub.2PO.sub.4).sub.3,
La(CO.sub.2H).sub.3, La(OR).sub.3, WCl.sub.2, WCl.sub.3, WCl.sub.4,
WCl.sub.5, WCl.sub.6, WBr.sub.2, WBr.sub.3, WBr.sub.4, WBr.sub.5,
WBr.sub.6, WI.sub.2, WI.sub.3, WI.sub.4, WI.sub.5, WI.sub.6,
W(NO.sub.3).sub.2, W(NO.sub.3).sub.3, W(NO.sub.3).sub.4,
W(NO.sub.3).sub.5, W(NO.sub.3).sub.6, W(CO.sub.2CH.sub.3).sub.2,
W(CO.sub.2CH.sub.3).sub.3, W(CO.sub.2CH.sub.3).sub.4,
W(CO.sub.2CH.sub.3).sub.5, W(CO.sub.2CH.sub.3).sub.6,
WC.sub.2O.sub.4, W.sub.2(C.sub.2O.sub.4).sub.3,
W(C.sub.2O.sub.4).sub.2, W.sub.2(C.sub.2O.sub.4).sub.5,
W(C.sub.2O.sub.4).sub.6, WPO.sub.4, W.sub.2(HPO.sub.4).sub.3,
W(H.sub.2PO.sub.4).sub.3, W(CO.sub.2H).sub.3, W(OR).sub.3,
W.sub.3(PO.sub.4).sub.4, W(HPO.sub.4).sub.2,
W(H.sub.2PO.sub.4).sub.4, W(CO.sub.2H).sub.4, W(OR).sub.4,
W.sub.3(PO.sub.4).sub.5, W.sub.2(HPO.sub.4).sub.5,
W(H.sub.2PO.sub.4).sub.5, W(CO.sub.2H).sub.5, W(OR).sub.5,
W(PO.sub.4).sub.2, W(HPO.sub.4).sub.3, W(H.sub.2PO.sub.4).sub.6,
W(CO.sub.2H).sub.6, W(OR).sub.6, MnCl.sub.2MnCl.sub.3,
MnBr.sub.2MnBr.sub.3, MnI.sub.2MnI.sub.3, Mn(NO.sub.3).sub.2,
Mn(NO.sub.3).sub.3, MnSO.sub.4, Mn.sub.2(SO.sub.4).sub.3,
Mn(CO.sub.2CH.sub.3).sub.2, Mn(CO.sub.2CH.sub.3).sub.3,
MnC.sub.2O.sub.4, Mn.sub.2(C.sub.2O.sub.4).sub.3,
Mn.sub.3(PO.sub.4).sub.2, MnHPO.sub.4, Mn(H.sub.2PO.sub.4).sub.2,
Mn(CO.sub.2H).sub.2, Mn(OR).sub.2, MnPO.sub.4,
Mn.sub.2(HPO.sub.4).sub.3, Mn(H.sub.2PO.sub.4).sub.3,
Mn(CO.sub.2H).sub.3, Mn(OR).sub.3, MoCl.sub.2, MoCl.sub.3,
MoCl.sub.4, MoCl.sub.5, MoBr.sub.2, MoBr.sub.3, MoBr.sub.4,
MoBr.sub.5, MoI.sub.2, MoI.sub.3, MoI.sub.4, MoI.sub.5,
Mo(NO.sub.3).sub.2, Mo(NO.sub.3).sub.3, Mo(NO.sub.3).sub.4,
Mo(NO.sub.3).sub.5, MoSO.sub.4, Mo.sub.2(SO.sub.4).sub.3,
Mo(SO.sub.4).sub.2, Mo.sub.2(SO.sub.4).sub.5,
Mo(CO.sub.2CH.sub.3).sub.2, Mo(CO.sub.2CH.sub.3).sub.3,
Mo(CO.sub.2CH.sub.3).sub.4, Mo(CO.sub.2CH.sub.3).sub.5,
MoC.sub.2O.sub.4, Mo.sub.2(C.sub.2O.sub.4).sub.3,
Mo(C.sub.2O.sub.4).sub.2, MO.sub.2(C.sub.2O.sub.4).sub.5,
Mo.sub.3(PO.sub.4).sub.2, MoHPO.sub.4, Mo(H.sub.2PO.sub.4).sub.2,
Mo(CO.sub.2H).sub.2, Mo(OR).sub.2, MoPO.sub.4,
MO.sub.2(HPO.sub.4).sub.3, Mo(H.sub.2PO.sub.4).sub.3,
Mo(CO.sub.2H).sub.3, Mo(OR).sub.3, Mo.sub.3(PO.sub.4).sub.4,
Mo(HPO.sub.4).sub.2, Mo(H.sub.2PO.sub.4).sub.4,
Mo(CO.sub.2H).sub.4, Mo(OR).sub.4, Mo.sub.3(PO.sub.4).sub.5,
Mo.sub.2(HPO.sub.4).sub.5, Mo(H.sub.2PO.sub.4).sub.5,
Mo(CO.sub.2H).sub.5, Mo(OR).sub.5, VCl, VCl.sub.2, VCl.sub.3,
VCl.sub.4, VCl.sub.5, VBr, VBr.sub.2, VBr.sub.3, VBr.sub.4,
VBr.sub.5, VI, VI.sub.2, VI.sub.3, VI.sub.4, VI.sub.5, VNO.sub.3,
V(NO.sub.3).sub.2, V(NO.sub.3).sub.3, V(NO.sub.3).sub.4,
V(NO.sub.3).sub.5, V.sub.2SO.sub.4, VSO.sub.4,
V.sub.2(SO.sub.4).sub.3, V(SO.sub.4).sub.4, VCO.sub.2CH.sub.3,
V(CO.sub.2CH.sub.3).sub.2, V(CO.sub.2CH.sub.3).sub.3,
V(CO.sub.2CH.sub.3).sub.4, V.sub.2C.sub.2O.sub.4, VC.sub.2O.sub.4,
V.sub.2(C.sub.2O.sub.4).sub.3, V(C.sub.2O.sub.4).sub.4,
V.sub.3PO.sub.4, V.sub.2HPO.sub.4, VH.sub.2PO.sub.4, VCO.sub.2H,
VOR, V.sub.3(PO.sub.4).sub.2, VHPO.sub.4, V(H.sub.2PO.sub.4).sub.2,
V(CO.sub.2H).sub.2, V(OR).sub.2, VPO.sub.4,
V.sub.2(HPO.sub.4).sub.3, V(H.sub.2PO.sub.4).sub.3,
V(CO.sub.2H).sub.3, V(OR).sub.3, V.sub.3(PO.sub.4).sub.4,
V(HPO.sub.4).sub.2, V(H.sub.2PO.sub.4).sub.4, V(CO.sub.2H).sub.4,
V(OR).sub.4, V.sub.3(PO.sub.4).sub.5, V.sub.2(HPO.sub.4).sub.5,
V(H.sub.2PO.sub.4).sub.5, V(CO.sub.2H).sub.5, V(OR).sub.5, TaCl,
TaCl.sub.2, TaCl.sub.3, TaCl.sub.4, TaCl.sub.5 TaBr, TaBr.sub.2,
TaBr.sub.3, TaBr.sub.4, TaBr.sub.5, TaI, TaI.sub.2, TaI.sub.3,
TaI.sub.4, TaI.sub.5, TaNO.sub.3, Ta(NO.sub.3).sub.2,
Ta(NO.sub.3).sub.3, Ta(NO.sub.3).sub.4, Ta(NO.sub.3).sub.5,
Ta.sub.2SO.sub.4, TaSO.sub.4, Ta.sub.2(SO.sub.4).sub.3,
Ta(SO.sub.4).sub.4, TaCO.sub.2CH.sub.3, Ta(CO.sub.2CH.sub.3).sub.2,
Ta(CO.sub.2CH.sub.3).sub.3, Ta(CO.sub.2CH.sub.3).sub.4,
Ta.sub.2C.sub.2O.sub.4, TaC.sub.2O.sub.4,
Ta.sub.2(C.sub.2O.sub.4).sub.3, Ta(C.sub.2O.sub.4).sub.4,
Ta.sub.3PO.sub.4, Ta.sub.2HPO.sub.4, TaH.sub.2PO.sub.4,
TaCO.sub.2H, TaOR, Ta.sub.3(PO.sub.4).sub.2, TaHPO.sub.4,
Ta(H.sub.2PO.sub.4).sub.2, Ta(CO.sub.2H).sub.2, Ta(OR).sub.2,
TaPO.sub.4, Ta.sub.2(HPO.sub.4).sub.3, Ta(H.sub.2PO.sub.4).sub.3,
Ta(CO.sub.2H).sub.3, Ta(OR).sub.3, Ta.sub.3(PO.sub.4).sub.4,
Ta(HPO.sub.4).sub.2, Ta(H.sub.2PO.sub.4).sub.4,
Ta(CO.sub.2H).sub.4, Ta(OR).sub.4, Ta.sub.3(PO.sub.4).sub.5,
Ta.sub.2(HPO.sub.4).sub.5, Ta(H.sub.2PO.sub.4).sub.5,
Ta(CO.sub.2H).sub.5, Ta(OR).sub.5, NbCl, NbCl.sub.2, NbCl.sub.3,
NbCl.sub.4, NbCl.sub.5 NbBr, NbBr.sub.2, NbBr.sub.3, NbBr.sub.4,
NbBr.sub.5, NbI, NbI.sub.2, NbI.sub.3, NbI.sub.4, NbI.sub.5,
NbNO.sub.3, Nb(NO.sub.3).sub.2, Nb(NO.sub.3).sub.3,
Nb(NO.sub.3).sub.4, Nb(NO.sub.3).sub.5, Nb.sub.2SO.sub.4,
NbSO.sub.4, Nb.sub.2(SO.sub.4).sub.3, Nb(SO.sub.4).sub.4,
NbCO.sub.2CH.sub.3, Nb(CO.sub.2CH.sub.3).sub.2,
Nb(CO.sub.2CH.sub.3).sub.3, Nb(CO.sub.2CH.sub.3).sub.4,
Nb.sub.2C.sub.2O.sub.4, NbC.sub.2O.sub.4,
Nb.sub.2(C.sub.2O.sub.4).sub.3, Nb(C.sub.2O.sub.4).sub.4,
Nb.sub.3PO.sub.4, Nb.sub.2HPO.sub.4, NbH.sub.2PO.sub.4,
NbCO.sub.2H, NbOR, Nb.sub.3(PO.sub.4).sub.2, NbHPO.sub.4,
Nb(H.sub.2PO.sub.4).sub.2, Nb(CO.sub.2H).sub.2, Nb(OR).sub.2,
NbPO.sub.4, Nb.sub.2(HPO.sub.4).sub.3, Nb(H.sub.2PO.sub.4).sub.3,
Nb(CO.sub.2H).sub.3, Nb(OR).sub.3, Nb.sub.3(PO.sub.4).sub.4,
Nb(HPO.sub.4).sub.2, Nb(H.sub.2PO.sub.4).sub.4,
Nb(CO.sub.2H).sub.4, Nb(OR).sub.4, Nb.sub.3(PO.sub.4).sub.5,
Nb.sub.2(HPO.sub.4).sub.5, Nb(H.sub.2PO.sub.4).sub.5,
Nb(CO.sub.2H).sub.5, Nb(OR).sub.5, NdCl.sub.3, NdBr.sub.3,
NdI.sub.3, Nd(NO.sub.3).sub.3, Nd.sub.2(SO.sub.4).sub.3,
Nd(CO.sub.2CH.sub.3).sub.3, Nd.sub.2(C.sub.2O.sub.4).sub.3,
NdPO.sub.4, Nd.sub.2(HPO.sub.4).sub.3, Nd(H.sub.2PO.sub.4).sub.3,
Nd(CO.sub.2H).sub.3, Nd(OR).sub.3, EuCl.sub.3, EuBr.sub.3,
EuI.sub.3, Eu(NO.sub.3).sub.3, Eu.sub.2(SO.sub.4).sub.3,
Eu(CO.sub.2CH.sub.3).sub.3, Eu.sub.2(C.sub.2O.sub.4).sub.3,
NdPO.sub.4, Nd.sub.2(HPO.sub.4).sub.3, Nd(H.sub.2PO.sub.4).sub.3,
Nd(CO.sub.2H).sub.3, Nd(OR).sub.3, PrCl.sub.3, PrBr.sub.3,
PrI.sub.3, Pr(NO.sub.3).sub.3, Pr.sub.2(SO.sub.4).sub.3,
Pr(CO.sub.2CH.sub.3).sub.3, Pr.sub.2(C.sub.2O.sub.4).sub.3,
PrPO.sub.4, Pr.sub.2(HPO.sub.4).sub.3, Pr(H.sub.2PO.sub.4).sub.3,
Pr(CO.sub.2H).sub.3, Pr(OR).sub.3, SmCl.sub.3, SmBr.sub.3,
SmI.sub.3, Sm(NO.sub.3).sub.3, Sm.sub.2(SO.sub.4).sub.3,
Sm(CO.sub.2CH.sub.3).sub.3, Sm.sub.2(C.sub.2O.sub.4).sub.3,
SmPO.sub.4, Sm.sub.2(HPO.sub.4).sub.3, Sm(H.sub.2PO.sub.4).sub.3,
Sm(CO.sub.2H).sub.3, Sm(OR).sub.3, CeCl.sub.3, CeBr.sub.3,
CeI.sub.3, Ce(NO.sub.3).sub.3, Ce.sub.2(SO.sub.4).sub.3,
Ce(CO.sub.2CH.sub.3).sub.3,
Ce.sub.2(C.sub.2O.sub.4).sub.3CePO.sub.4,
Ce.sub.2(HPO.sub.4).sub.3, Ce(H.sub.2PO.sub.4).sub.3,
Ce(CO.sub.2H).sub.3, Ce(OR).sub.3, or combinations thereof, wherein
R is alkyl, alkenyl, alkynyl or aryl.
[0408] In more specific embodiments, the metal salt comprises
MgCl.sub.2, LaCl.sub.3, ZrCl.sub.4, WCl.sub.4, MoCl.sub.4,
MnCl.sub.2MnCl.sub.3, Mg(NO.sub.3).sub.2, La(NO.sub.3).sub.3,
ZrOCl.sub.2, Mn(NO.sub.3).sub.2, Mn(NO.sub.3).sub.3,
ZrO(NO.sub.3).sub.2, Zr(NO.sub.3).sub.4, or combinations
thereof.
[0409] In other embodiments, the metal salt comprises NdCl.sub.3,
NdBr.sub.3, NdI.sub.3, Nd(NO.sub.3).sub.3,
Nd.sub.2(SO.sub.4).sub.3, Nd(CO.sub.2CH.sub.3).sub.3,
Nd.sub.2(C.sub.2O.sub.4).sub.3, EuCl.sub.3, EuBr.sub.3, EuI.sub.3,
Eu(NO.sub.3).sub.3, Eu.sub.2(SO.sub.4).sub.3,
Eu(CO.sub.2CH.sub.3).sub.3, Eu.sub.2(C.sub.2O.sub.4).sub.3,
PrCl.sub.3, PrBr.sub.3, PrI.sub.3, Pr(NO.sub.3).sub.3,
Pr.sub.2(SO.sub.4).sub.3, Pr(CO.sub.2CH.sub.3).sub.3,
Pr.sub.2(C.sub.2O.sub.4).sub.3 or combinations thereof.
[0410] In still other embodiments, the metal salt comprises Mg, Ca,
Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures thereof. The salt may
be in the form of (oxy)chlorides, (oxy)nitrates or tungstates.
[0411] (c) Anion Precursor
[0412] The anions, or counter ions of the metal ions that nucleate
on the template, are provided in the form of an anion precursor.
The anion precursor dissociates in the solution phase and releases
an anion. Thus, the anion precursor can be any stable soluble salts
having the desired anion. For instance, bases such as alkali metal
hydroxides (e.g., sodium hydroxide, lithium hydroxide, potassium
hydroxides) and ammonium hydroxide are anion precursors that
provide hydroxide ions for nucleation. Alkali metal carbonates
(e.g., sodium carbonate, potassium carbonates) and ammonium
carbonate are anion precursors that provide carbonates ions for
nucleation.
[0413] In certain embodiments, the anion precursor comprises one or
more metal hydroxide, metal carbonate, metal bicarbonate, metal
sulfate, metal phosphate or metal oxalate. Preferably, the metal is
an alkali or an alkaline earth metal. Thus, the anion precursor may
comprise any one of alkali metal hydroxides, carbonates,
bicarbonates, sulfates, phosphates or oxalate; or any one of
alkaline earth metal hydroxides, carbonates, bicarbonates,
sulfates, phosphates or oxalates.
[0414] In some specific embodiments, the one or more anion
precursors comprise LiOH, NaOH, KOH, Sr(OH).sub.2, Ba(OH).sub.2,
Na.sub.2CO.sub.3, K.sub.2CO.sub.3, NaHCO.sub.3,
KHCO.sub.3(NR.sub.4).sub.2CO.sub.3, and NR.sub.4OH, wherein each R
is independently selected from H, C.sub.1-C.sub.18 alkyl,
C.sub.1-C.sub.18 alkenyl, C.sub.1-C.sub.18 alkynyl and
C.sub.1-C.sub.18 aryl. Ammonium salts may provide certain
advantages in that there is less possibility of introducing
unwanted metal impurities. Accordingly, in a further embodiment,
the anion precursor comprises ammonium hydroxide or ammonium
carbonate.
[0415] The dimensions of the nanowires are comparable to those of
the polymer templates, although they can have different aspect
ratios as longer growth can be used to increase the diameter while
the length will increase in size at a much slower rate. The spacing
of monomers on the polymer surface controls the nucleation location
and the catalytic nanowire size based on steric hindrance. The
monomer identity can (or may) dictate the identity, size, shape and
crystalline face of the catalytic nanowire being nucleated. To
achieve the desired stochiometry between metal elements, support
and dopants, polymers comprising multiple monomers specific for
these discrete materials can be used. Alternatively, precursor
salts for the materials can be combined in the reaction at the
desired stochiometry
[0416] 3. Core/Shell Structures
[0417] In certain embodiments, nanowires can be grown on a support
nanowire that has no or a different catalytic property. FIG. 7
shows an exemplary process 600 for growing a core/shell nanowire
structure. Similar to the process described in FIG. 7, a polymer
solution is prepared (block 604), to which a first metal salt and a
first anion precursor are sequentially added (blocks 610 and 620)
in appropriate conditions to allow for the nucleation and growth of
a nanowire (M1.sub.m1X1.sub.n1Z.sub.p1) on the polymer (block 624).
Thereafter, a second metal salt and a second anion precursor are
sequentially added (blocks 630 and 634), under conditions to cause
the nucleation and growth of a coating of
M2.sub.m2X2.sub.n2Z.sub.p2 on the nanowire
M1.sub.m1X1.sub.n1Z.sub.p1 (block 640). Following calcinations,
nanowires of a core/shell structure
M1.sub.x1O.sub.y1/M2.sub.x2O.sub.y2 are formed, wherein x1, y1, x2
and y2 are each independently a number from 1 to 100, and p1 and p2
are each independently a number from 0 to 100 (block 644). A
further step of impregnation (block 650) produces a nanowire
comprising a dopant and comprising a core of M1.sub.x1O.sub.y1
coated with a shell of M2.sub.x2O.sub.y2. For ease of illustration,
FIG. 7 depicts calcinations prior to doping; however, in certain
embodiments doping may be performed prior to calcinations. In some
embodiments, M1 is Mg, Al, Ga, Ca or Zr. In certain embodiments of
the foregoing, M1 is Mn and M2 is Mg. In other embodiments, M1 is
Mg and M2 is Mn. In other embodiments, M1 is La and M2 is Mg, Ca,
Sr, Ba, Zr, Nd, Y, Yb, Eu, Sm or Ce. In other embodiments, M1 is Mg
and M2 is La or Nd.
[0418] In other embodiments, M1.sub.x1O.sub.y1 comprises
La.sub.2O.sub.3 while in other embodiments M2.sub.x2O.sub.y2
comprises La.sub.2O.sub.3. In other embodiments of the foregoing,
M1.sub.x1O.sub.y1 or M2.sub.x2O.sub.y2 further comprises a dopant,
wherein the dopant comprises Nd, Mn, Fe, Zr, Sr, Ba, Y or
combinations thereof. Other specific combinations of core/shell
nanowires are also envisioned within the scope of the present
disclosure.
[0419] Thus, one embodiment provides a method for preparing metal
oxide, metal oxy-hydroxide, metal oxycarbonate or metal carbonate
nanowires in a core/shell structure, the method comprising:
[0420] (a) providing a solution that includes a plurality of
polymer templates;
[0421] (b) introducing a first metal ion and a first anion to the
solution under conditions and for a time sufficient to allow for
nucleation and growth of a first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1) on the template; and
[0422] (c) introducing a second metal ion and optionally a second
anion to the solution under conditions and for a time sufficient to
allow for nucleation and growth of a second nanowire
(M2.sub.m2X2.sub.n2Z.sub.p2) on the first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1);
[0423] (d) converting the first nanowire
(M1.sub.m1X1.sub.n1Z.sub.p1) and the second nanowire
(M2.sub.m2X2.sub.n2Z.sub.2) to the respective metal oxide nanowires
(M1.sub.x1O.sub.y1) and (M2.sub.x2O.sub.y2), the respective metal
oxy-hydroxide nanowires (M1.sub.x1O.sub.y1OH.sub.z1) and
(M2.sub.x2O.sub.y2OH.sub.z2) the respective metal oxycarbonate
nanowires (M1.sub.x1O.sub.y1(CO.sub.3).sub.z1) and
(M2.sub.x2O.sub.y2(CO.sub.3).sub.z2) or the respective metal
carbonate nanowires (M1.sub.x1(CO.sub.3).sub.y1) and
(M2.sub.x2(CO.sub.3).sub.y2),
[0424] wherein:
[0425] M1 and M2 are the same or different and independently
selected from a metal element;
[0426] X1 and X2 are the same or different and independently
hydroxides, carbonates, bicarbonates, phosphates,
hydrogenphosphates, dihydrogenphosphates, sulfates, nitrates or
oxalates;
[0427] Z is O;
[0428] n1, m1, n2, m2, x1, y1, z1, x2, y2 and z2 are each
independently a number from 1 to 100; and
[0429] p1 and p2 are independently a number from 0 to 100.
[0430] In some embodiments, M1 and M2 are the same or different and
independently selected from a metal element from any of Groups 2
through 7, lanthanides or actinides
[0431] In various embodiments, the polymer templates are are
selected from PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol),
PEI (polyethyleneimine), PEG (polyethyleneglycol), polyether,
polyesters, polyamides, dextran and other sugar polymers,
functionalized hydrocarbon polymers, functionalized polystyrene,
polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene
glycol)-poly(propylene glycol)-poly(ethylene glycol) and copolymers
and combinations thereof. In some embodiments, the polymer template
is functionalized with at least one of amine, carboxylic acid,
sulfate, alcohol, halogen or thiol groups. For example the polymer
template may be a hydrocarbon or polystyrene polymer functionalized
with at least one of amine, carboxylic acid, sulfate, alcohol,
halogen or thiol groups.
[0432] In some embodiments, the nanowire is dried in an oven, while
in other embodiments the nanowire is freeze dried or air dried. The
drying method may have an effect on the final morphology, pore
size, etc. of the resulting nanowire. Additionally, the solution
comprising the polymer template may be in the form of a gel and the
metal ions are impregnated therein. The gel may then be dried as
described above. In some different embodiments, the polymer
template is removed from the nanowire by heat treatment or other
removal means.
[0433] In further embodiments, the respective metal ion is provided
by adding one or more respective metal salts (as described herein)
to the solution. In other embodiments, the respective anions are
provided by adding one or more respective anion precursors to the
solution. In various embodiments, the first metal ion and the first
anion can be introduced to the solution simultaneously or
sequentially in any order. Similarly, the second metal ion and
optionally the second anion can be introduced to the solution
simultaneously or sequentially in any order. The first and second
nanowire are typically converted to a metal oxide, metal
oxy-hydroxide, metal oxycarbonate or metal carbonate nanowire in a
core/shell structure by calcination.
[0434] In yet another embodiment, the method further comprises
doping the metal oxide nanowire in a core/shell structure with a
dopant.
[0435] By varying the nucleation conditions, including the pH of
the solution, relative ratio of metal salt precursors and the anion
precursors, relative ratios of the precursors and the polymer of
the synthetic mixture, stable nanowires of diverse compositions and
surface properties can be prepared.
[0436] In certain embodiments, the core nanowire (the first
nanowire) is not catalytically active or less so than the shell
nanowire (the second nanowire), and the core nanowire serve as an
intrinsic catalytic support for the more active shell nanowire. For
example, ZrO.sub.2 may not have high catalytic activity in an OCM
reaction, whereas Sr.sup.2+ doped La.sub.2O.sub.3 does. A ZrO.sub.2
core thus may serve as a support for the catalytic Sr.sup.2+ doped
La.sub.2O.sub.3 shell.
[0437] In some embodiments, the present disclosure provides a
nanowire comprising a core/shell structure and comprising a ratio
of effective length to actual length of less than one. In other
embodiments, the nanowires having a core/shell structure comprise a
ratio of effective length to actual length equal to one.
[0438] 4. Diversity
[0439] As noted above, in some embodiments, the disclosed
template-directed synthesis provides nanowires having diverse
compositions and/or morphologies. This method enables production of
a library of nanowire catalysts with a new level of control over
materials composition, materials surface and crystal structure.
These nanowires prepared by polymer-templated methods take
advantage of the large variation of different polymer structures
and sizes, etc. to enable combinatorial synthesis of robust, active
and selective inorganic catalytic polycrystalline nanowires.
Modification of the various synthetic parameters permits
simultaneous optimization of the nanowires' catalytic properties in
a high-dimensional space.
[0440] In various embodiments, the synthetic parameters for
nucleating and growing nanowires can be manipulated to create
nanowires of diverse compositions and morphologies. Typical
synthetic parameters include, without limitation, concentration
ratios of metal ions and active functional groups on the polymer
(e.g., various monomers); concentration ratios of metal and anions
(e.g., hydroxide); incubation time of polymer and metal salt;
incubation time of polymer and anion; concentration of polymer;
sequence of adding anion and metal ions; pH; polymer composition
and size; solution temperature in the incubation step and/or growth
step; types of metal precursor salt; types of anion precursor;
addition rate, number of additions; the time that lapses between
the additions of the metal salt and anion precursor, including,
e.g., simultaneous (zero lapse) or sequential additions followed by
respective incubation times for the metal salt and the anion
precursor.
[0441] Additional variable synthetic parameters include, growth
time once both metal and anion are present in the solution; choice
of solvents (although water is typically used, certain amounts of
alcohol, such as methanol, ethanol and propanol, can be mixed with
water); choice and the number of metal salts used (e.g., both
LaCl.sub.3 and La(NO.sub.3).sub.3 can be used to provide La.sup.3+
ions); choice and the number of anion precursors used (e.g., both
NaOH then LiOH can be used to provide the hydroxide); choice or the
number of different polymers used; the presence or absence of a
buffer solution; the different stages of the growing step (e.g.,
nanowires may be precipitated and cleaned and resuspended in a
second solution and perform a second growth of the same material
(thicker core) or different material to form a core/shell
structure.
[0442] Thus, libraries of nanowires can be generated with diverse
physical properties and characteristics such as: composition, e.g.,
basic metal oxides (M.sub.xO.sub.y), size, shape, surface
morphology, exposed crystal faces/edge density, crystallinity,
dispersion, and stoichiometry and nanowire template physical
characteristics including length, width, porosity and pore density.
High throughput, combinatorial screening methods are then applied
to evaluate the catalytic performance characteristics of the
nanowires (see, e.g., FIG. 2). Based on these results, lead target
candidates are identified. From these lead targets, further
rational modifications to the synthetic designs can be made to
create nanowires that satisfy certain catalytic performance
criteria. This results in further refinement of the nanowire design
and material structure.
Catalytic Reactions
[0443] The present disclosure provides for the use of catalytic
nanowires as catalysts in catalytic reactions and related methods.
In some embodiments, the catalytic reaction is any of the reactions
described herein. The morphology and composition of the catalytic
nanowires is not limited, and the nanowires may be prepared by any
method. For example the nanowires may have a bent morphology or a
straight morphology and may have any molecular composition. In some
embodiments, the nanowires have better catalytic properties than a
corresponding bulk catalyst (i.e., a catalyst having the same
chemical composition as the nanowire, but prepared from bulk
material). In some embodiments, the nanowire having better
catalytic properties than a corresponding bulk catalyst has a ratio
of effective length to actual length equal to one. In other
embodiments, the nanowire having better catalytic properties than a
corresponding bulk catalyst has a ratio of effective length to
actual length of less than one. In other embodiments, the nanowire
having better catalytic properties than a corresponding bulk
catalyst comprises one or more elements from Groups 1 through 7,
lanthanides or actinides.
[0444] Nanowires may be useful in any number of reactions catalyzed
by a heterogeneous catalyst. Examples of reactions wherein
nanowires having catalytic activity may be employed are disclosed
in Farrauto and Bartholomew, "Fundamentals of Industrial Catalytic
Processes" Blackie Academic and Professional, first edition, 1997,
which is hereby incorporated in its entirety. Other non-limiting
examples of reactions wherein nanowires having catalytic activity
may be employed include: the oxidative coupling of methane (OCM) to
ethane and ethylene; oxidative dehydrogenation (ODH) of alkanes to
the corresponding alkenes, for example oxidative dehydrogenation of
ethane or propane to ethylene or propylene, respectively; selective
oxidation of alkanes, alkenes, and alkynes; oxidation of CO, dry
reforming of methane, selective oxidation of aromatics;
Fischer-Tropsch, hydrocarbon cracking; combustion of hydrocarbons
and the like. Reactions catalyzed by the disclosed nanowires are
discussed in more detail below.
[0445] The nanowires are generally useful as catalysts in methods
for converting a first carbon-containing compound (e.g., a
hydrocarbon, CO or CO.sub.2) to a second carbon-containing
compound. In some embodiments the methods comprise contacting a
nanowire, or material comprising the same, with a gas comprising a
first carbon-containing compound and an oxidant to produce a
carbon-containing compound. In some embodiments, the first
carbon-containing compound is a hydrocarbon, CO, CO.sub.2, methane,
ethane, propane, hexane, cyclohexane, octane or combinations
thereof. In other embodiments, the second carbon-containing
compound is a hydrocarbon, CO, CO.sub.2, ethane, ethylene, propane,
propylene, hexane, hexene, cyclohexane, cyclohexene, bicyclohexane,
octane, octene or hexadecane. In some embodiments, the oxidant is
oxygen, ozone, nitrous oxide, nitric oxide, carbon dioxide, water
or combinations thereof.
[0446] In other embodiments of the foregoing, the method for
conversion of a first carbon-containing compound to a second
carbon-containing compound is performed at a temperature below
100.degree. C., below 200.degree. C., below 300.degree. C., below
400.degree. C., below 500.degree. C., below 600.degree. C., below
700.degree. C., below 800.degree. C., below 900.degree. C. or below
1000.degree. C. In other embodiments, the method for conversion of
a first carbon-containing compound to a second carbon-containing
compound is performed at a pressure above 0.5 ATM, above 1 ATM,
above 2 ATM, above 5 ATM, above 10 ATM, above 25 ATM or above 50
ATM.
[0447] The catalytic reactions described herein can be performed
using standard laboratory equipment known to those of skill in the
art, for example as described in U.S. Pat. No. 6,350,716, which is
incorporated herein in its entirety.
[0448] As noted above, the nanowires disclosed herein have better
catalytic activity than a corresponding bulk catalyst. In some
embodiments, the selectivity, yield, conversion, or combinations
thereof, of a reaction catalyzed by the nanowires is better than
the selectivity, yield, conversion, or combinations thereof, of the
same reaction catalyzed by a corresponding bulk catalyst under the
same conditions. For example, in some embodiments, the nanowire
possesses a catalytic activity such that conversion of reactant to
product in a reaction catalyzed by the nanowire is greater than at
least 1.1 times, greater than at least 1.25 times, greater than at
least 1.5 times, greater than at least 2.0 times, greater than at
least 3.0 times or greater than at least 4.0 times the conversion
of reactant to product in the same reaction catalyzed by a catalyst
prepared from bulk material having the same chemical composition as
the nanowire.
[0449] In other embodiments, the nanowire possesses a catalytic
activity such that selectivity for product in a reaction catalyzed
by the nanowire is greater than at least 1.1 times, greater than at
least 1.25 times, greater than at least 1.5 times, greater than at
least 2.0 times, greater than at least 3.0 times, or greater than
at least 4.0 times the selectivity for product in the same reaction
under the same conditions but catalyzed by a catalyst prepared from
bulk material having the same chemical composition as the
nanowire.
[0450] In yet other embodiments, the nanowire possesses a catalytic
activity such that yield of product in a reaction catalyzed by the
nanowire is greater than at least 1.1 times, greater than at least
1.25 times, greater than at least 1.5 times, greater than at least
2.0 times, greater than at least 3.0 times, or greater than at
least 4.0 times the yield of product in the same reaction under the
same conditions but catalyzed by a catalyst prepared from bulk
material having the same chemical composition as the nanowire.
[0451] In yet other embodiments, the nanowire possesses a catalytic
activity such that activation temperature of a reaction catalyzed
by the nanowire is at least 25.degree. C. lower, at least
50.degree. C. lower, at least 75.degree. C. lower, or at least
100.degree. C. lower than the temperature of the same reaction
under the same conditions but catalyzed by a catalyst prepared from
bulk material having the same chemical composition as the
nanowire.
[0452] In certain reactions (e.g., OCM), production of unwanted
oxides of carbon (e.g., CO and CO.sub.2) is a problem that reduces
overall yield of desired product and results in an environmental
liability. Accordingly, in one embodiment the present disclosure
addresses this problem and provides nanowires with a catalytic
activity such that the selectivity for CO and/or CO.sub.2 in a
reaction catalyzed by the nanowires is less than the selectivity
for CO and/or CO.sub.2 in the same reaction under the same
conditions but catalyzed by a corresponding bulk catalyst.
Accordingly, in one embodiment, the present disclosure provides a
nanowire which possesses a catalytic activity such that selectivity
for CO.sub.x, wherein x is 1 or 2, in a reaction catalyzed by the
nanowire is less than at least 0.9 times, less than at least 0.8
times, less than at least 0.5 times, less than at least 0.2 times
or less than at least 0.1 times the selectivity for CO.sub.x in the
same reaction under the same conditions but catalyzed by a catalyst
prepared from bulk material having the same chemical composition as
the nanowire.
[0453] In some embodiments, the absolute selectivity, yield,
conversion, or combinations thereof, of a reaction catalyzed by the
nanowires disclosed herein is better than the absolute selectivity,
yield, conversion, or combinations thereof, of the same reaction
under the same conditions but catalyzed by a corresponding bulk
catalyst. For example, in some embodiments the yield of product in
a reaction catalyzed by the nanowires is greater than 20%, greater
than 30%, greater than 50%, greater than 75%, or greater than 90%.
In other embodiments, the selectivity for product in a reaction
catalyzed by the nanowires is greater than 20%, greater than 30%,
greater than 50%, greater than 75%, or greater than 90%. In other
embodiments, the conversion of reactant to product in a reaction
catalyzed by the nanowires is greater than 20%, greater than 30%,
greater than 50%, greater than 75%, or greater than 90%.
[0454] In addition to the improved catalytic performance of the
disclosed nanowires, the morphology of the nanowires is expected to
provide for improved mixing properties for the nanowires compared
to standard colloidal (e.g., bulk) catalyst materials. The improved
mixing properties are expected to improve the performance of any
number of catalytic reactions, for example, in the area of
transformation of heavy hydrocarbons where transport and mixing
phenomena are known to influence the catalytic activity. In other
reactions, the shape of the nanowires is expected to provide for
good blending, reduce settling, and provide for facile separation
of any solid material.
[0455] In some other chemical reactions, the nanowires are useful
for absorption and/or incorporation of a reactant used in chemical
looping. For example, the nanowires find utility as NO.sub.x traps,
in unmixed combustion schemes, as oxygen storage materials, as
CO.sub.2 sorption materials (e.g., cyclic reforming with high
H.sub.2 output) and in schemes for conversion of water to
H.sub.2.
[0456] 1. Oxidative Coupling of Methane (OCM)
[0457] As noted above, the present disclosure provides nanowires
having catalytic activity and related approaches to nanowire design
and preparation for improving the yield, selectivity and/or
conversion of any number of catalyzed reactions, including the OCM
reaction. As mentioned above, there exists a tremendous need for
catalyst technology capable of addressing the conversion of methane
into high value chemicals (e.g., ethylene and products prepared
therefrom) using a direct route that does not go through syngas.
Accomplishing this task will dramatically impact and redefine a
non-petroleum based pathway for feedstock manufacturing and liquid
fuel production yielding reductions in GHG emissions, as well as
providing new fuel sources.
[0458] Ethylene has the largest carbon footprint compared to all
industrial chemical products in part due to the large total volume
consumed into a wide range of downstream important industrial
products including plastics, surfactants and pharmaceuticals. In
2008, worldwide ethylene production exceeded 120 M metric tons
while growing at a robust rate of 4% per year. The United States
represents the largest single producer at 28% of the world
capacity. Ethylene is primarily manufactured from high temperature
cracking of naphtha (e.g., oil) or ethane that is separated from
natural gas. The true measurement of the carbon footprint can be
difficult as it depends on factors such as the feedstock and the
allocation as several products are made and separated during the
same process. However, some general estimates can be made based on
published data.
[0459] Cracking consumes a significant portion (about 65%) of the
total energy used in ethylene production and the remainder is for
separations using low temperature distillation and compression. The
total tons of CO.sub.2 emission per ton of ethylene are estimated
at between 0.9 to 1.2 from ethane cracking and 1 to 2 from naphtha
cracking. Roughly, 60% of ethylene produced is from naphtha, 35%
from ethane and 5% from others sources (Ren, T.; Patel, M. Res.
Conserv. Recycl. 53:513, 2009). Therefore, based on median
averages, an estimated amount of CO.sub.2 emissions from the
cracking process is 114M tons per year (based on 120M tons
produced). Separations would then account for an additional 61 M
tons CO.sub.2 per year.
[0460] Nanowires provide an alternative to the need for the energy
intensive cracking step. Additionally, because of the high
selectivity of the nanowires, downstream separations are
dramatically simplified, as compared to cracking which yields a
wide range of hydrocarbon products. The reaction is also exothermic
so it can proceed via an autothermal process mechanism. Overall, it
is estimated that up to a potential 75% reduction in CO.sub.2
emission compared to conventional methods could be achieved. This
would equate to a reduction of one billion tons of CO.sub.2 over a
ten-year period and would save over 1M barrels of oil per day.
[0461] The nanowires also permit converting ethylene into liquid
fuels such as gasoline or diesel, given ethylene's high reactivity
and numerous publications demonstrating high yield reactions, in
the lab setting, from ethylene to gasoline and diesel. On a life
cycle basis from well to wheel, recent analysis of methane to
liquid (MTL) using F-T process derived gasoline and diesel fuels
has shown an emission profile approximately 20% greater to that of
petroleum based production (based on a worst case scenario)
(Jaramillo, P., Griffin, M., Matthews, S., Env. Sci. Tech 42:7559,
2008). In the model, the CO.sub.2 contribution from plant energy
was a dominating factor at 60%. Thus, replacement of the cracking
and F-T process would be expected to provide a notable reduction in
net emissions, and could be produced at lower CO.sub.2 emissions
than petroleum based production.
[0462] Furthermore, a considerable portion of natural gas is found
in regions that are remote from markets or pipelines. Most of this
gas is flared, re-circulated back into oil reservoirs, or vented
given its low economic value. The World Bank estimates flaring adds
400M metric tons of CO.sub.2 to the atmosphere each year as well as
contributing to methane emissions. The nanowires of this disclosure
also provide economic and environmental incentive to stop flaring.
Also, the conversion of methane to fuel has several environmental
advantages over petroleum-derived fuel. Natural gas is the cleanest
of all fossil fuels, and it does not contain a number of impurities
such as mercury and other heavy metals found in oil. Additionally,
contaminants including sulfur are also easily separated from the
initial natural gas stream. The resulting fuels burn much cleaner
with no measurable toxic pollutants and provide lower emissions
than conventional diesel and gasoline in use today.
[0463] In view of its wide range of applications, the nanowires of
this disclosure can be used to not only selectively activate
alkanes, but also to activate other classes of inert unreactive
bonds, such as C--F, C--Cl or C--O bonds. This has importance, for
example, in the destruction of man-made environmental toxins such
as CFCs, PCBs, dioxins and other pollutants. Accordingly, while the
invention is described in greater detail below in the context of
the OCM reaction and other the other reactions described herein,
the nanowire catalysts are not in any way limited to this
particular reaction.
[0464] The selective, catalytic oxidative coupling of methane to
ethylene (i.e. the OCM reaction) is shown by the following reaction
(1):
2CH.sub.4+O.sub.2.fwdarw.CH.sub.2CH.sub.2+2H.sub.2O (1)
This reaction is exothermic (Heat of Reaction-67 kcals/mole) and
usually occurs at very high temperatures (>700.degree. C.).
During this reaction, it is believed that the methane (CH.sub.4) is
first oxidatively coupled into ethane (C.sub.2H.sub.6), and
subsequently the ethane (C.sub.2H.sub.6) is oxidatively
dehydrogenated into ethylene (C.sub.2H.sub.4). Because of the high
temperatures used in the reaction, it has been suggested that the
ethane is produced mainly by the coupling in the gas phase of the
surface-generated methyl (CH.sub.3) radicals. Reactive metal oxides
(oxygen type ions) are apparently required for the activation of
CH.sub.4 to produce the CH.sub.3 radicals. The yield of
C.sub.2H.sub.4 and C.sub.2H.sub.6 is limited by further reactions
in the gas phase and to some extent on the catalyst surface. A few
of the possible reactions that occur during the oxidation of
methane are shown below as reactions (2) through (8):
CH.sub.4.fwdarw.CH.sub.3 radical (2)
CH.sub.3 radical.fwdarw.C.sub.2H.sub.6 (3)
CH.sub.3 radical+2.5O.sub.2.fwdarw.CO.sub.2+1.5H.sub.2O (4)
C.sub.2H.sub.6.fwdarw.C.sub.2H.sub.4+H.sub.2 (5)
C.sub.2H.sub.6+0.5O.sub.2.fwdarw.C.sub.2H.sub.4+H.sub.2O (6)
C.sub.2H.sub.4+3O.sub.2.fwdarw.2CO.sub.2+2H.sub.2O (7)
CH.sub.3 radical+C.sub.xH.sub.y+O.sub.2.fwdarw.Higher
HC's-Oxidation/CO.sub.2+H.sub.2O (8)
[0465] With conventional heterogeneous catalysts and reactor
systems, the reported performance is generally limited to <25%
CH.sub.4 conversion at <80% combined C.sub.2 selectivity, with
the performance characteristics of high selectivity at low
conversion, or the low selectivity at high conversion. In contrast,
the nanowires of this disclosure are highly active and can
optionally operate at a much lower temperature. In one embodiment,
the nanowires disclosed herein enable efficient conversion of
methane to ethylene in the OCM reaction at temperatures less than
when the corresponding bulk material is used as a catalyst. For
example, in one embodiment, the nanowires disclosed herein enable
efficient conversion (i.e., high yield, conversion, and/or
selectivity) of methane to ethylene at temperatures of less than
900.degree. C., less than 800.degree. C., less than 700.degree. C.,
less than 600.degree. C., or less than 500.degree. C. In other
embodiments, the use of staged oxygen addition, designed heat
management, rapid quench and/or advanced separations may also be
employed.
[0466] Accordingly, one embodiment of the present disclosure is a
method for the preparation of ethan and/or ethylene, the method
comprising converting methane to ethan and/or ethylene in the
presence of a catalytic material, wherein the catalytic material
comprises at least one catalytic nanowire as disclosed herein.
[0467] Accordingly, in one embodiment a stable, very active, high
surface area, multifunctional nanowire catalyst is disclosed having
active sites that are isolated and precisely engineered with the
catalytically active metal centers/sites in the desired proximity
(see, e.g., FIG. 1).
[0468] The exothermic heats of reaction (free energy) follow the
order of reactions depicted above and, because of the proximity of
the active sites, will mechanistically favor ethylene formation
while minimizing complete oxidation reactions that form CO and
CO.sub.2. Representative nanowire compositions useful for the OCM
reaction include, but are not limited to: highly basic oxides
selected from the early members of the Lanthanide oxide series;
Group 1 or 2 ions supported on basic oxides, such as Li/MgO, Ba/MgO
and Sr/La.sub.2O.sub.3; and single or mixed transition metal
oxides, such as VO.sub.X and Re/Ru that may also contain Group 1
ions. Other nanowire compositions useful for the OCM reaction
comprise any of the compositions disclosed herein, for example MgO,
La.sub.2O.sub.3, Na.sub.2WO.sub.4, Mn.sub.2O.sub.3,
Mn.sub.3O.sub.4, Mg.sub.6MnO.sub.8, Zr.sub.2Mo.sub.2O.sub.8,
NaMnO.sub.4, Mn.sub.2O.sub.3/Na.sub.2WO.sub.4,
Mn.sub.3O.sub.4/Na.sub.2WO.sub.4 or Na/MnO.sub.4/MgO, Mn/WO4,
Nd.sub.2O.sub.3, Sm.sub.2O.sub.3, Eu.sub.2O.sub.3 or combinations
thereof. Activating promoters (i.e., dopants), such as chlorides,
nitrates and sulfates, or any of the dopants described above may
also be employed.
[0469] As noted above, the presently disclosed nanowires comprise a
catalytic performance better than corresponding bulk catalysts, for
example in one embodiment the catalytic performance of the
nanowires in the OCM reaction is better than the catalytic
performance of a corresponding bulk catalyst. In this regard,
various performance criteria may define the "catalytic performance"
of the catalysts in the OCM (and other reactions). In one
embodiment, catalytic performance is defined by C2 selectivity in
the OCM reaction, and the C2 selectivity of the nanowires in the
OCM reaction is >5%, >10%, >15%, >20%, >25%,
>30%, >35%, >40%, >45%, >50%, >55%, >60%,
>65%, >70%, >75% or >80%.
[0470] Other important performance parameters used to measure the
nanowires' catalytic performace in the OCM reaction are selected
from single pass methane conversion percentage (i.e., the percent
of methane converted on a single pass over the catalyst or
catalytic bed, etc.), reaction inlet gas temperature, reaction
operating temperature, total reaction pressure, methane partial
pressure, gas-hour space velocity (GHSV), O.sub.2 source, catalyst
stability and ethylene to ethane ratio. In certain embodiments,
improved catalytic performance is defined in terms of the
nanowires' improved performance (relative to a corresponding bulk
catalyst) with respect to at least one of the foregoing performance
parameters.
[0471] The reaction inlet gas temperature in an OCM reaction
catalyzed by the disclosed nanowires can generally be maintained at
a lower temperature, while maintaining better performance
characteristics (e.g., conversion, C2 yield, C2 selctivity and the
like) compared to the same reaction catalyzed by a corresponding
bulk catalyst under the same reaction conditions. In certain
embodiments, the inlet gas temperature in an OCM reaction catalyzed
by the disclosed nanowires is <700.degree. C., <675.degree.
C., <650.degree. C., <625.degree. C., <600.degree. C.,
<593.degree. C., <580.degree. C., <570.degree. C.,
<560.degree. C., <550.degree. C., <540.degree. C.,
<530.degree. C., <520.degree. C., <510.degree. C.,
<500.degree. C., <490.degree. C., <480.degree. C. or even
<470.degree. C.
[0472] The reaction operating temperature in an OCM reaction
catalyzed by the disclosed nanowires can generally be maintained at
a lower temperature, while maintaining better performance
characteristics compared to the same reaction catalyzed by a
corresponding bulk catalyst under the same reaction conditions. In
certain embodiments, the reaction operating temperature in an OCM
reaction catalyzed by the disclosed nanowires is <700.degree.
C., <675.degree. C., <650.degree. C., <625.degree. C.,
<600.degree. C., <593.degree. C., <580.degree. C.,
<570.degree. C., <560.degree. C., <550.degree. C.,
<540.degree. C., <530.degree. C., <520.degree. C.,
<510.degree. C., <500.degree. C., <490.degree. C.,
<480.degree. C., <470.degree. C.
[0473] The single pass methane conversion in an OCM reaction
catalyzed by the nanowires is also generally better compared to the
single pass methane conversion in the same reaction catalyzed by a
corresponding bulk catalyst under the same reaction conditions. For
single pass methane conversion it is preferably >5%, >10%,
>15%, >20%, >25%, >30%, >35%, >40%, >45%,
>50%, >55%, >60%, >65%, >70%, >75%, >80%.
[0474] In certain embodiments, the total reaction pressure in an
OCM reaction catalyzed by the nanowires is >1 atm, >1.1 atm,
>1.2 atm, >1.3 atm, >1.4 atm, >1.5 atm, >1.6 atm,
>1.7 atm, >1.8 atm, >1.9 atm, >2 atm, >2.1 atm,
>2.1 atm, >2.2 atm, >2.3 atm, >2.4 atm, >2.5 atm,
>2.6 atm, >2.7 atm, >2.8 atm, >2.9 atm, >3.0 atm,
>3.5 atm, >4.0 atm, >4.5 atm, >5.0 atm, >5.5 atm,
>6.0 atm, >6.5 atm, >7.0 atm, >7.5 atm, >8.0 atm,
>8.5 atm, >9.0 atm, >10.0 atm, >11.0 atm, >12.0 atm,
>13.0 atm, >14.0 atm, >15.0 atm, >16.0 atm, >17.0
atm, >18.0 atm, >19.0 atm or >20.0 atm.
[0475] In some embodiments, the methane partial pressure in an OCM
reaction catalyzed by the nanowires is >0.3 atm, >0.4 atm,
>0.5 atm, >0.6 atm, >0.7 atm, >0.8 atm, >0.9 atm,
>1 atm, >1.1 atm, >1.2 atm, >1.3 atm, >1.4 atm,
>1.5 atm, >1.6 atm, >1.7 atm, >1.8 atm, >1.9 atm,
>2.0 atm, >2.1 atm, >2.2 atm, >2.3 atm, >2.4 atm,
>2.5 atm, >2.6 atm, >2.7 atm, >2.8 atm, >2.9 atm,
>3.0 atm, >3.5 atm, >4.0 atm, >4.5 atm, >5.0 atm,
>5.5 atm, >6.0 atm, >6.5 atm, >7.0 atm, >7.5 atm,
>8.0 atm, >8.5 atm, >9.0 atm, >10.0 atm, >11.0 atm,
>12.0 atm, >13.0 atm, >14.0 atm, >15.0 atm, >16.0
atm, >17.0 atm, >18.0 atm, >19.0 atm or >20.0 atm.
[0476] In some embodiments, the GSHV in an OCM reaction catalyzed
by the nanowires is >20,000/hr, >50,000/hr, >75,000/hr,
>100,000/hr, >120,000/hr, >130,000/hr, >150,000/hr,
>200,000/hr, >250,000/hr, >300,000/hr, >350,000/hr,
>400,000/hr, >450,000/hr, >500,000/hr, >750,000/hr,
>1,000,000/hr, >2,000,000/hr, >3,000,000/hr,
>4,000,000/hr.
[0477] In contrast to other OCM reactions, the present inventors
have discovered that OCM reactions catalyzed by the disclosed
nanowires can be performed (and still maintain high C2 yield, C2
selectivity, conversion, etc.) using O.sub.2 sources other than
pure O.sub.2. For example, in some embodiments the O.sub.2 source
in an OCM reaction catalyzed by the disclosed nanowires is air,
oxygen enriched air, pure oxygen, oxygen diluted with nitrogen (or
another inert gas) or oxygen diluted with CO.sub.2. In certain
embodiments, the O.sub.2 source is O.sub.2 diluted by >99%,
>98%, >97%, >96%, >95%, >94%, >93%, >92%,
>91%, >90%, >85%, >80%, >75%, >70%, >65%,
>60%, >55%, >50%, >45%, >40%, >35%, >30%,
>25%, >20%, >15%, >10%, >9%, >8%, >7%, >6%,
>5%, >4%, >3%, >2% or >1% with CO.sub.2 or an inert
gas, for example nitrogen.
[0478] The disclosed nanowires are also very stable under
conditions required to perform any number of catalytic reactions,
for example the OCM reaction. The stability of the nanowires is
defined as the length of time a catalyst will maintain its
catalytic performance without a significant decrease in performance
(e.g., a decrease >20%, >15%, >10%, >5%, or greater
than 1% in C2 yield, C2 selectivity or conversion, etc.). In some
embodiments, the nanowires have stability under conditions required
for the OCM reaction of >1 hr, >5 hrs, >10 hrs, >20
hrs, >50 hrs, >80 hrs, >90 hrs, >100 hrs, >150 hrs,
>200 hrs, >250 hrs, >300 hrs, >350 hrs, >400 hrs,
>450 hrs, >500 hrs, >550 hrs, >600 hrs, >650 hrs,
>700 hrs, >750 hrs, >800 hrs, >850 hrs, >900 hrs,
>950 hrs, >1,000 hrs, >2,000 hrs, >3,000 hrs, >4,000
hrs, >5,000 hrs, >6,000 hrs, >7,000 hrs, >8,000 hrs,
>9,000 hrs, >10,000 hrs, >11,000 hrs, >12,000 hrs,
>13,000 hrs, >14,000 hrs, >15,000 hrs, >16,000 hrs,
>17,000 hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs,
>1 yrs, >2 yrs, >3 yrs, >4 yrs or >5 yrs.
[0479] In some embodiments, the ratio of ethylene to ethane in an
OCM reaction catalyzed by the nanowires is better than the ratio of
ethylene to ethane in an OCM reaction catalyzed by a corresponding
bulk catalyst under the same conditions. In some embodiments, the
ratio of ethylene to ethane in an OCM reaction catalyzed by the
nanowires is >0.3, >0.4, >0.5, >0.6, >0.7, >0.8,
>0.9, >1, >1.1, >1.2, >1.3, >1.4, >1.5,
>1.6, >1.7, >1.8, >1.9, >2.0, >2.1, >2.2,
>2.3, >2.4, >2.5, >2.6, >2.7, >2.8, >2.9,
>3.0, >3.5, >4.0, >4.5, >5.0, >5.5, >6.0,
>6.5, >7.0, >7.5, >8.0, >8.5, >9.0, >9.5,
>10.0.
[0480] As noted above, the OCM reaction employing known bulk
catalysts suffers from poor yield, selectivity, or conversion. In
contrast to a corresponding bulk catalyst, Applicants have found
that certain nanowires, for example the exemplary nanowires
disclosed herein, posses a catalytic activity in the OCM reaction
such that the yield, selectivity, and/or conversion is better than
when the OCM reaction is catalyzed by a corresponding bulk
catalyst. In one embodiment, the disclosure provides a nanowire
having a catalytic activity such that the conversion of methane to
ethylene in the oxidative coupling of methane reaction is greater
than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0
times, or 4.0 times the conversion of methane to ethylene compared
to the same reaction under the same conditions but performed with a
catalyst prepared from bulk material having the same chemical
composition as the nanowire. In other embodiments, the conversion
of methane to ethylene in an OCM reaction catalyzed by the nanowire
is greater than 10%, greater than 20%, greater than 30%, greater
than 50%, greater than 75%, or greater than 90%.
[0481] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the yield of ethylene in the
oxidative coupling of methane reaction is greater than at least 1.1
times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times
the yield of ethylene compared to the same reaction under the same
conditions but performed with a catalyst prepared from bulk
material having the same chemical composition as the nanowire. In
some embodiments the yield of ethylene in an OCM reaction catalyzed
by the nanowire is greater than 10%, greater than 20%, greater than
30%, greater than 50%, greater than 75%, or greater than 90%.
[0482] As noted above, the OCM reaction employing known bulk
catalysts suffers from poor yield, selectivity, or conversion. In
contrast to a corresponding bulk catalyst, Applicants have found
that certain nanowires, for example the exemplary nanowires
disclosed herein, posses a catalytic activity in the OCM reaction
such that the yield, selectivity, and/or conversion is better than
when the OCM reaction is catalyzed by a corresponding bulk
catalyst. In one embodiment, the disclosure provides a nanowire
having a catalytic activity such that the conversion of methane in
the oxidative coupling of methane reaction is greater than at least
1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0
times the conversion of methane compared to the same reaction under
the same conditions but performed with a catalyst prepared from
bulk material having the same chemical composition as the nanowire.
In other embodiments, the conversion of methane in an OCM reaction
catalyzed by the nanowire is greater than 10%, greater than 20%,
greater than 30%, greater than 50%, greater than 75%, or greater
than 90%.
[0483] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the C2 yield in the oxidative
coupling of methane reaction is greater than at least 1.1 times,
1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the C2
yield compared to the same reaction under the same conditions but
performed with a catalyst prepared from bulk material having the
same chemical composition as the nanowire. In some embodiments the
C2 yield in an OCM reaction catalyzed by the nanowire is greater
than 10%, greater than 20%, greater than 30%, greater than 50%,
greater than 75%, or greater than 90%.
[0484] In another embodiment, the disclosure provides a nanowire
having a catalytic activity in the OCM reaction such that the
nanowire has the same catalytic activity (i.e., same selectivity,
conversion or yield), but at a lower temperature, compared a
catalyst prepared from bulk material having the same chemical
composition as the nanowire. In some embodiments the catalytic
activity of the nanowires in the OCM reaction is the same as the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 20.degree. C. less. In some embodiments the catalytic
activity of the nanowires in the OCM reaction is the same as the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 50.degree. C. less. In some embodiments the catalytic
activity of the nanowires in the OCM reaction is the same as the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 100.degree. C. less. In some embodiments the catalytic
activity of the nanowires in the OCM reaction is the same as the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 200.degree. C. less.
[0485] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the selectivity for CO or
CO.sub.2 in the oxidative coupling of methane reaction is less than
at least 0.9 times, 0.8 times, 0.5 times, 0.2 times, or 0.1 times
the selectivity for CO or CO.sub.2 compared to the same reaction
under the same conditions but performed with a catalyst prepared
from bulk material having the same chemical composition as the
nanowire.
[0486] In some other embodiments, a method for converting methane
into ethylene comprising use of catalyst mixture comprising two or
more catalysts is provided. For example, the catalyst mixture may
be a mixture of a catalyst having good OCM activity and a catalyst
having good ODH activity. Such catalyst mixture are described in
more detail above.
[0487] Typically, the OCM reaction is run in a mixture of oxygen
and nitrogen or other inert gas. Such gasses are expensive and
increase the overall production costs associated with preparation
of ethylene or ethane from methane. However, the present inventors
have now discovered that such expensive gases are not required and
high yield, conversion, selectivity, etc. can be obtained when air
is used as the gas mixture instead of pre-packaged and purified
sources of oxygen and other gases. Accordingly, in one embodiment
the disclosure provides a method for performing the OCM reaction in
air.
[0488] In addition to air or O.sub.2 gas, the presently disclosed
nanowires and associated methods provide for use of other sources
of oxygen in the OCM reaction. In this respect, an alternate source
of oxygen such a CO.sub.2, H.sub.2O, SO.sub.2 or SO.sub.3 may be
used either in place of, or in addition to, air or oxygen as the
oxygen source. Such methods have the potential to increase the
efficiency of the OCM reaction, for example by consuming a reaction
byproduct (e.g., CO.sub.2 or H.sub.2O) and controlling the OCM
exotherm as described below.
[0489] As noted above, in the OCM reaction, methane is oxidatively
converted to methyl radicals, which are then coupled to form
ethane, which is subsequently oxidized to ethylene. In traditional
OCM reactions, the oxidation agent for both the methyl radical
formation and the ethane oxidation to ethylene is oxygen. In order
to minimize full oxidation of methane or ethane to carbon dioxide,
i.e. maximize C2 selectivity, the methane to oxygen ratio is
generally kept at 4 (i.e. full conversion of methane into methyl
radicals) or above. As a result, the OCM reaction is typically
oxygen limited and thus the oxygen concentration in the effluent is
zero.
[0490] Accordingly, in one embodiment the present disclosure
provides a method for increasing the methane conversion and
increasing, or in some embodiments, not reducing, the C2
selectivity in an OCM reaction. The disclosed methods include
adding to a traditional OCM catalyst another OCM catalyst that uses
an oxygen source other than molecular oxygen. In some embodiments,
the alternate oxygen source is CO.sub.2, H.sub.2O, SO.sub.2,
SO.sub.3 or combinations thereof. For example in some embodiments,
the alternate oxygen source is CO.sub.2. In other embodiments the
alternate oxygen source is H.sub.2O.
[0491] Because C2 selectivity is typically between 50% and 80% in
the OCM reaction, OCM typically produces significant amounts of
CO.sub.2 as a byproduct (CO.sub.2 selectivity can typically range
from 20-50%). Additionally, H.sub.2O is produced in copious
amounts, regardless of the C2 selectivity. Therefore both CO.sub.2
and H.sub.2O would are attractive oxygen sources for OCM in an
O.sub.2 depleted environment.
[0492] Accordingly, one embodiment of the present disclosure
provides a catalyst (and related methods for use thereof) which is
catalytic in the OCM reaction and which uses CO.sub.2, H.sub.2O,
SO.sub.2, SO.sub.3 or another alternative oxygen source or
combinations thereof as a source of oxygen. Other embodiments,
provide a catalytic material comprising two or more catalysts,
wherein the catalytic material comprises at least one catalyst
which is catalytic in the OCM reaction and uses O.sub.2 for at
least one oxygen source and at least one catalysts which is
catalytic in the OCM reaction and uses at least of CO.sub.2,
H.sub.2O, SO.sub.2, SO.sub.3, NO, NO.sub.2, NO.sub.3 or another
alternative oxygen source. Methods for performing the OCM reaction
with such catalytic materials are also provided. Such catalysts
comprise any of the compositions disclosed herein and are effective
as catalysts in an OCM reaction using an alternative oxygen source
at temperatures of 900.degree. C. or lower, 850.degree. C. or
lower, 800.degree. C. or lower, 750.degree. C. or lower,
700.degree. C. or lower or even 650.degree. C. or lower. In some
embodiments of the above, the catalyst is a nanowire catalyst.
[0493] Examples of OCM catalysts that use CO.sub.2 or other oxygen
sources rather than O.sub.2 include, but are not limited to,
catalysts comprising La.sub.2O.sub.3/ZnO, CeO.sub.2/ZnO, CaO/ZnO,
CaO/CeO.sub.2, CaO/Cr.sub.2O.sub.3, CaO/MnO.sub.2, SrO/ZnO,
SrO/CeO.sub.2, SrO/Cr.sub.2O.sub.3, SrO/MnO.sub.2,
SrCO.sub.3/MnO.sub.2, BaO/ZnO, BaO/CeO.sub.2, BaO/Cr.sub.2O.sub.3,
BaO/MnO.sub.2, CaO/MnO/CeO.sub.2, Na.sub.2WO.sub.4/Mn/SiO.sub.2,
Pr.sub.2O.sub.3, Tb.sub.2O.sub.3.
[0494] Some embodiments provide a method for performing OCM,
wherein a mixture of an OCM catalyst which use O.sub.2 as an oxygen
source (referred to herein as an O.sub.2-OCM catalyst) and an OCM
catalyst which use CO.sub.2 as an oxygen source (referred to herein
as a CO.sub.2-OCM catalyst) is employed as the catalytic material,
for example in a catalyst bed. Such methods have certain
advantages. For example, the CO.sub.2-OCM reaction is endothermic
and the O.sub.2-OCM reaction is exothermic, and thus if the right
mixture and/or arrangement of CO.sub.2-OCM and O.sub.2-OCM
catalysts is used, the methods are particularly useful for
controlling the exotherm of the OCM reaction. In some embodiments,
the catalyst bed comprises a mixture of O.sub.2-OCM catalyst and
CO.sub.2-OCM catalysts. The mixture may be in a ratio of 1:99 to
99:1. The two catalysts work synergistically as the O.sub.2-OCM
catalyst supplies the CO.sub.2-OCM catalyst with the necessary
carbon dioxide and the endothermic nature of the C.sub.2-OCM
reaction serves to control the exotherm of the overall reaction.
Alternatively, the CO.sub.2 source may be external to the reaction
(e.g., fed in from a CO.sub.2 tank, or other source) and/or the
heat required for the CO.sub.2-OCM reaction is supplied from an
external source (e.g., heating the reactor).
[0495] Since the gas composition will tend to become enriched in
CO.sub.2 as it flows through the catalyst bed (i.e., as the OCM
reaction proceeds, more CO.sub.2 is produced), some embodiments of
the present invention provide an OCM method wherein the catalyst
bed comprises a gradient of catalysts which changes from a high
concentration of O.sub.2-OCM catalysts at the front of the bed to a
high concentration of CO.sub.2-OCM catalysts at the end of the
catalyst bed.
[0496] The O.sub.2-OCM catalyst and CO.sub.2 OCM catalyst may have
the same or different compositions. For example, in some
embodiments the O.sub.2-OCM catalyst and CO.sub.2-OCM catalyst have
the same composition but different morphologies (e.g., nanowire,
bent nanowire, bulk, etc.). In other embodiments the O.sub.2-OCM
and the CO.sub.2-OCM catalyst have different compositions.
[0497] Furthermore, CO.sub.2-OCM catalysts will typically have
higher selectivity, but lower yields than an O.sub.2-OCM catalyst.
Accordingly, in one embodiment the methods comprise use of a
mixture of an O.sub.2-OCM catalyst and a CO.sub.2-OCM catalyst and
performing the reaction in O.sub.2 deprived environment so that the
CO.sub.2-OCM reaction is favored and the selectivity is increased.
Under appropriate conditions the yield and selectivity of the OCM
reaction can thus be optimized.
[0498] In some other embodiments, the catalyst bed comprises a
mixture of one or more low temperature O.sub.2-OCM catalyst (i.e.,
a catalyst active at low temperatures, for example less than
700.degree. C.) and one or more high temperature CO.sub.2-OCM
catalyst (i.e., a catalyst active at high temperatures, for example
800.degree. C. or higher). Here, the required high temperature for
the CO.sub.2-OCM may be provided by the hotspots produced by the
O.sub.2-OCM catalyst. In such a scenario, the mixture may be
sufficiently coarse such that the hotspots are not being
excessively cooled down by excessive dilution effect.
[0499] In other embodiments, the catalyst bed comprises alternating
layers of O.sub.2-OCM and CO.sub.2-OCM catalysts. The catalyst
layer stack may begin with a layer of O.sub.2-OCM catalyst, so that
it can supply the next layer (e.g., a CO.sub.2-OCM layer) with the
necessary CO.sub.2. The O.sub.2-OCM layer thickness may be
optimized to be the smallest at which O.sub.2 conversion is 100%
and thus the CH.sub.4 conversion of the layer is maximized. The
catalyst bed may comprise any number of catalyst layers, for
example the overall number of layers may be optimized to maximize
the overall CH.sub.4 conversion and C2 selectivity.
[0500] In some embodiments, the catalyst bed comprises alternating
layers of low temperature O.sub.2-OCM catalysts and high
temperature CO.sub.2-OCM catalysts. Since the CO.sub.2-OCM reaction
is endothermic, the layers of CO.sub.2-OCM catalyst may be
sufficiently thin such that in can be "warmed up" by the hotspots
of the O.sub.2-OCM layers. The endothermic nature of the
CO.sub.2-OCM reaction can be advantageous for the overall thermal
management of an OCM reactor. In some embodiments, the CO.sub.2-OCM
catalyst layers act as "internal" cooling for the O.sub.2-OCM
layers, thus simplifying the requirements for the cooling, for
example in a tubular reactor. Therefore, an interesting cycle takes
place with the endothermic reaction providing the necessary heat
for the endothermic reaction and the endothermic reaction providing
the necessary cooling for the exothermic reaction.
[0501] Accordingly, one embodiment of the present invention is a
method for the oxidative coupling of methane, wherein the method
comprises conversion of methane to ethane and/or ethylene in the
presence of a catalytic material, and wherein the catalytic
material comprises a bed of alternating layers of O.sub.2-OCM
catalysts and CO.sub.2-OCM catalysts. In other embodiments the bed
comprises a mixture (i.e., not alternating layers) of O.sub.2-OCM
catalysts and CO.sub.2-OCM catalysts.
[0502] In other embodiments, the OCM methods include use of a
jacketed reactor with the exothermic O.sub.2-OCM reaction in the
core and the endothermic CO.sub.2-OCM reaction in the mantel. In
other embodiments, the unused CO.sub.2 can be recycled and
reinjected into the reactor, optionally with the recycled CH.sub.4.
Additional CO.sub.2 can also be injected to increase the overall
methane conversion and help reduce greenhouse gases.
[0503] In other embodiments, the reactor comprises alternating
stages of O.sub.2-OCM catalyst beds and CO.sub.2-OCM catalyst beds.
The CO.sub.2 necessary for the CO.sub.2-OCM stages is provided by
the O.sub.2-OCM stage upstream. Additional CO.sub.2 may also be
injected. The O.sub.2 necessary for the subsequent O.sub.2-OCM
stages is injected downstream from the CO.sub.2-OCM stages. The
CO.sub.2-OCM stages may provide the necessary cooling for the
O.sub.2-OCM stages. Alternatively, separate cooling may be
provided. Likewise, if necessary the inlet gas of the CO.sub.2-OCM
stages can be additionally heated, the CO.sub.2-OCM bed can be
heated or both.
[0504] In related embodiments, the CO.sub.2 naturally occurring in
natural gas is not removed prior to performing the OCM,
alternatively CO2 is added to the feed with the recycled methane.
Instead the CO.sub.2 containing natural gas is used as a feedstock
for CO.sub.2-OCM, thus potentially saving a separation step. The
amount of naturally occurring CO.sub.2 in natural gas depends on
the well and the methods can be adjusted accordingly depending on
the source of the natural gas.
[0505] The foregoing methods can be generalized as a method to
control the temperature of very exothermic reactions by coupling
them with an endothermic reaction that uses the same feedstock (or
byproducts of the exothermic reaction) to make the same product (or
a related product). This concept can be reversed, i.e. providing
heat to an endothermic reaction by coupling it with an exothermic
reaction. This will also allow a higher per pass yield in the OCM
reactor.
[0506] For purpose of simplicity, the above description relating to
the use of O.sub.2-OCM and CO.sub.2-OCM catalysts was described in
reference to the oxidative coupling of methane (OCM); however, the
same concept is applicable to other catalytic reactions including
but not limited to: oxidative dehydrogenation (ODH) of alkanes to
their corresponding alkenes, selective oxidation of alkanes and
alkenes and alkynes, etc. For example, in a related embodiment, a
catalyst capable of using an alternative oxygen source (e.g.,
CO.sub.2, H.sub.2O, SO.sub.2, SO.sub.3 or combinations thereof) to
catalyze the oxidative dehydrogenation of ethane is provided. Such
catalysts, and uses thereof are described in more detail below.
[0507] Furthermore, the above methods are applicable for creating
novel catalysts by blending catalysts that use different reactants
for the same catalytic reactions, for example different oxidants
for an oxidation reaction and at least one oxidant is a byproduct
of one of the catalytic reactions. In addition, the methods can
also be generalized for internal temperature control of reactors by
blending catalysts that catalyze reactions that share the same or
similar products but are exothermic and endothermic, respectively.
These two concepts can also be coupled together.
[0508] 2. Oxidative Dehydrogenation
[0509] Worldwide demand for alkenes, especially ethylene and
propylene, is high. The main sources for alkenes include steam
cracking, fluid-catalytic-cracking and catalytic dehydrogenation.
The current industrial processes for producing alkenes, including
ethylene and propylene, suffer from some of the same disadvantages
described above for the OCM reaction. Accordingly, a process for
the preparation of alkenes, which is more energy efficient and has
higher yield, selectivity, and conversion than current processes is
needed. Applicants have now found that nanowires, for example the
exemplary nanowires disclosed herein, fulfill this need and provide
related advantages.
[0510] In one embodiment, the disclosed nanowires are useful as
catalysts for the oxidative dehydrogenation (ODH) of hydrocarbons
(e.g. alkanes, alkenes, and alkynes). For example, in one
embodiment the nanowires are useful as catalysts in an ODH reaction
for the conversion of ethane or propane to ethylene or propylene,
respectively. Reaction scheme (9) depicts the oxidative
dehydrogenation of hydrocarbons:
C.sub.xH.sub.y+1/2O.sub.2.fwdarw.C.sub.xH.sub.y-2+H.sub.2O (9)
[0511] Representative catalysts useful for the ODH reaction
include, but are not limited to nanowires comprising Zr, V, Mo, Ba,
Nd, Ce, Ti, Mg, Nb, La, Sr, Sm, Cr, W, Y or Ca or oxides or
combinations thereof. Activating promoters (i.e. dopants)
comprising P, K, Ca, Ni, Cr, Nb, Mg, Au, Zn, or Mo, or combinations
thereof, may also be employed.
[0512] As noted above, improvements to the yield, selectivity,
and/or conversion in the ODH reaction employing bulk catalysts are
needed. Accordingly, in one embodiment, the present disclosure
provides a nanowire which posses a catalytic activity in the ODH
reaction such that the yield, selectivity, and/or conversion is
better than when the ODH reaction is catalyzed by a corresponding
bulk catalyst. In one embodiment, the disclosure provides a
nanowire having a catalytic activity such that the conversion of
hydrocarbon to alkene in the ODH reaction is greater than at least
1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0
times the conversion of alkane to alkene compared to the same
reaction under the same conditions but performed with a catalyst
prepared from bulk material having the same chemical composition as
the nanowire. In other embodiments, the conversion of hydrocarbon
to alkene in an ODH reaction catalyzed by the nanowire is greater
than 10%, greater than 20%, greater than 30%, greater than 50%,
greater than 75%, or greater than 90%.
[0513] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the yield of alkene in an ODH
reaction is greater than at least 1.1 times, 1.25 times, 1.50
times, 2.0 times, 3.0 times, or 4.0 times the yield of alkenes
compared to the same reaction under the same conditions but
performed with a catalyst prepared from bulk material having the
same chemical composition as the nanowire. In some embodiments the
yield of alkene in an ODH reaction catalyzed by the nanowire is
greater than 10%, greater than 20%, greater than 30%, greater than
50%, greater than 75%, or greater than 90%.
[0514] In another embodiment, the disclosure provides a nanowire
having a catalytic activity in the ODH reaction such that the
nanowire has the same catalytic activity, but at a lower
temperature, compared a catalyst prepared from bulk material having
the same chemical composition as the nanowire. In some embodiments
the catalytic activity of the nanowires in the ODH reaction is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 20.degree. C. less. In
some embodiments the catalytic activity of the nanowires in the ODH
reaction is the same or better than the catalytic activity of a
catalyst prepared from bulk material having the same chemical
composition as the nanowire, but at a temperature of at least
50.degree. C. less. In some embodiments the catalytic activity of
the nanowires in the ODH reaction is the same or better than the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 100.degree. C. less. In some embodiments the catalytic
activity of the nanowires in the ODH reaction is the same or better
than the catalytic activity of a catalyst prepared from bulk
material having the same chemical composition as the nanowire, but
at a temperature of at least 200.degree. C. less.
[0515] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the selectivity for alkenes
in an ODH reaction is greater than at least 1.1 times, 1.25 times,
1.50 times, 2.0 times, 3.0 times, or 4.0 times the selectivity for
alkenes compared to the same reaction under the same conditions but
performed with a catalyst prepared from bulk material having the
same chemical composition as the nanowire. In other embodiments,
the selectivity for alkenes in an ODH reaction catalyzed by the
nanowire is greater than 50%, greater than 60%, greater than 70%,
greater than 80%, greater than 90%, or greater than 95%.
[0516] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the selectivity for CO or
CO.sub.2 in an ODH reaction is less than at least 0.9 times, 0.8
times, 0.5 times, 0.2 times, or 0.1 times the selectivity for CO or
CO.sub.2 compared to the same reaction under the same conditions
but performed with a catalyst prepared from bulk material having
the same chemical composition as the nanowire.
[0517] In one embodiment, the nanowires disclosed herein enable
efficient conversion of hydrocarbon to alkene in the ODH reaction
at temperatures less than when the corresponding bulk material is
used as a catalyst. For example, in one embodiment, the nanowires
disclosed herein enable efficient conversion (i.e. high yield,
conversion, and/or selectivity) of hydrocarbon to alkene at
temperatures of less than 800.degree. C., less than 700.degree. C.,
less than 600.degree. C., less than 500.degree. C., less than
400.degree. C., or less than 300.degree. C.
[0518] The stability of the nanowires is defined as the length of
time a catalyst will maintain its catalytic performance without a
significant decrease in performance (e.g., a decrease >20%,
>15%, >10%, >5%, or greater than 1% in ODH activity or
alkene selectivity, etc.). In some embodiments, the nanowires have
stability under conditions required for the ODH reaction of >1
hr, >5 hrs, >10 hrs, >20 hrs, >50 hrs, >80 hrs,
>90 hrs, >100 hrs, >150 hrs, >200 hrs, >250 hrs,
>300 hrs, >350 hrs, >400 hrs, >450 hrs, >500 hrs,
>550 hrs, >600 hrs, >650 hrs, >700 hrs, >750 hrs,
>800 hrs, >850 hrs, >900 hrs, >950 hrs, >1,000 hrs,
>2,000 hrs, >3,000 hrs, >4,000 hrs, >5,000 hrs,
>6,000 hrs, >7,000 hrs, >8,000 hrs, >9,000 hrs,
>10,000 hrs, >11,000 hrs, >12,000 hrs, >13,000 hrs,
>14,000 hrs, >15,000 hrs, >16,000 hrs, >17,000 hrs,
>18,000 hrs, >19,000 hrs, >20,000 hrs, >1 yrs, >2
yrs, >3 yrs, >4 yrs or >5 yrs.
[0519] As noted above, one embodiment of the present disclosure is
directed to a catalyst capable of using an alternative oxygen
source (e.g., CO.sub.2, H.sub.2O, SO.sub.2, SO.sub.3 or
combinations thereof) to catalyze the oxidative dehydrogenation of
ethane is provided. For example, the ODH reaction may proceed
according to the following reaction (10):
CO.sub.2+C.sub.xH.sub.y.fwdarw.C.sub.xH.sub.y-2+CO+H.sub.2O
(10)
wherein x is an interger and Y is 2x+2. Compositions useful in this
regard include Fe.sub.2O.sub.3, Cr.sub.2O.sub.3, MnO.sub.2,
Ga.sub.2O.sub.3, Cr/SiO.sub.2, Cr/SO.sub.4--SiO.sub.2,
Cr--K/SO.sub.4--SiO.sub.2, Na.sub.2WO.sub.4--Mn/SiO.sub.2,
Cr-HZSM-5, Cr/Si-MCM-41 (Cr-HZSM-5 and Cr/Si-MCM-41 refer to known
zeolites) and MoC/SiO.sub.2. In some embodiments, any of the
foregoing catalyst compositions may be supported on SiO.sub.2,
ZrO.sub.2, Al.sub.2O.sub.3, TiO.sub.2 or combinations thereof. In
certain embodiments, the catalyst may be a nanowire catalyst and in
other embodiments the catalyst is a bulk catalyst.
[0520] The catalysts having ODH activity with alternative oxygen
sources (e.g., CO.sub.2, referred to herein as a CO.sub.2-ODH
catalyst) have a number of advantages. For example, in some
embodiments a method for converting methane to ethylene comprises
use of an O.sub.2-OCM catalyst in the presence of a CO.sub.2-ODH
catalyst is provided. Catalytic materials comprising at least one
O.sub.2-OCM catalyst and at least one CO.sub.2-ODH catalyst are
also provided in some embodiments. This combination of catalysts
results in a higher yield of ethylene (and/or ratio of ethylene to
ethane) since the CO.sub.2 produced by the OCM reaction is consumed
and used to convert ethane to ethylene.
[0521] In one embodiment, a method for preparation of ethylene
comprises converting methane to ethylene in the presence of two or
more catalysts, wherein at least one catalyst is an O.sub.2-OCM
catalyst and at least one catalyst is a CO.sub.2-ODH catalyst. Such
methods have certain advantages. For example, the CO2-ODH reaction
is endothermic and the O.sub.2-OCM reaction is exothermic, and thus
if the right mixture and/or arrangement of CO.sub.2-ODH and
O.sub.2-OCM catalysts is used, the methods are particularly useful
for controlling the exotherm of the OCM reaction. In some
embodiments, the catalyst bed comprises a mixture of O.sub.2-OCM
catalyst and CO2-ODH catalysts. The mixture may be in a ratio of
1:99 to 99:1. The two catalysts work synergistically as the
O.sub.2-OCM catalyst supplies the CO.sub.2-ODH catalyst with the
necessary carbon dioxide and the endothermic nature of the
C.sub.2-OCM reaction serves to control the exotherm of the overall
reaction.
[0522] Since the gas composition will tend to become enriched in
CO.sub.2 as it flows through the catalyst bed (i.e., as the OCM
reaction proceeds, more CO.sub.2 is produced), some embodiments of
the present invention provide an OCM method wherien the catalyst
bed comprises a gradient of catalysts which changes from a high
concentration of O.sub.2-OCM catalysts at the front of the bed to a
high concentration of CO.sub.2-ODH catalysts at the end of the
catalyst bed.
[0523] The O.sub.2-ODH catalyst and CO.sub.2-ODH catalyst may have
the same or different compositions. For example, in some
embodiments the O.sub.2-ODH catalyst and CO.sub.2-ODH catalyst have
the same composition but different morphologies (e.g., nanowire,
bent nanowire, bulk, etc.). In other embodiments the O.sub.2-ODH
and the CO.sub.2-ODH catalyst have different compositions.
[0524] In other embodiments, the catalyst bed comprises alternating
layers of O.sub.2-OCM and CO.sub.2-ODH catalysts. The catalyst
layer stack may begin with a layer of O.sub.2-OCM catalyst, so that
it can supply the next layer (e.g., a CO2-ODH layer) with the
necessary CO.sub.2. The O.sub.2-OCM layer thickness may be
optimized to be the smallest at which O2 conversion is 100% and
thus the CH.sub.4 conversion of the layer is maximized. The
catalyst bed may comprise any number of catalyst layers, for
example the overall number of layers may be optimized to maximize
the overall CH.sub.4 conversion and C2 selectivity.
[0525] In some embodiments, the catalyst bed comprises alternating
layers of low temperature O.sub.2-OCM catalysts and high
temperature CO.sub.2-ODH catalysts. Since the CO.sub.2-ODH reaction
is endothermic, the layers of CO.sub.2-ODH catalyst may be
sufficiently thin such that in can be "warmed up" by the hotspots
of the O.sub.2-OCM layers. The endothermic nature of the
CO.sub.2-ODH reaction can be advantageous for the overall thermal
management of an OCM reactor. In some embodiments, the CO.sub.2-ODH
catalyst layers act as "internal" cooling for the O.sub.2-OCM
layers, thus simplifying the requirements for the cooling, for
example in a tubular reactor. Therefore, an interesting cycle takes
place with the endothermic reaction providing the necessary heat
for the endothermic reaction and the endothermic reaction providing
the necessary cooling for the exothermic reaction.
[0526] Accordingly, one embodiment of the present invention is a
method for the oxidative coupling of methane, wherein the method
comprises conversion of methane to ethane and/or ethylene in the
presence of a catalytic material, and wherein the catalytic
material comprises a bed of alternating layers of O.sub.2-OCM
catalysts and CO.sub.2-ODH catalysts. In other embodiments the bed
comprises a mixture (i.e., not alternating layers) of O.sub.2-OCM
catalysts and CO.sub.2-ODH catalysts. Such methods increase the
ethylene yield and/or ratio of ethylene to ethane compared to other
known methods.
[0527] In other embodiments, the OCM methods include use of a
jacketed reactor with the exothermic O.sub.2-OCM reaction in the
core and the endothermic CO.sub.2-ODH reaction in the mantel. In
other embodiments, the unused CO.sub.2 can be recycled and
reinjected into the reactor, optionally with the recycled CH.sub.4.
Additional CO.sub.2 can also be injected to increase the overall
methane conversion and help reduce greenhouse gases.
[0528] In other embodiments, the reactor comprises alternating
stages of O.sub.2-OCM catalyst beds and CO.sub.2-ODH catalyst beds.
The CO.sub.2 necessary for the CO.sub.2-ODH stages is provided by
the O.sub.2-OCM stage upstream. Additional CO.sub.2 may also be
injected. The O.sub.2 necessary for the subsequent O2-OCM stages is
injected downstream from the CO.sub.2-ODH stages. The CO.sub.2-ODH
stages may provide the necessary cooling for the O.sub.2-OCM
stages. Alternatively, separate cooling may be provided. Likewise,
if necessary the inlet gas of the CO.sub.2-ODH stages can be
additionally heated, the CO.sub.2-ODH bed can be heated or
both.
[0529] In related embodiments, the CO.sub.2 naturally occurring in
natural gas is not removed prior to performing the OCM,
alternatively CO.sub.2 is added to the feed with the recycled
methane. Instead the CO.sub.2 containing natural gas is used as a
feedstock for CO.sub.2-ODH, thus potentially saving a separation
step. The amount of naturally occurring CO.sub.2 in natural gas
depends on the well and the methods can be adjusted accordingly
depending on the source of the natural gas.
[0530] 3. Carbon dioxide reforming of methane
[0531] Carbon dioxide reforming (CDR) of methane is an attractive
process for converting CO.sub.2 in process streams or naturally
occurring sources into the valuable chemical product, syngas (a
mixture of hydrogen and carbon monoxide). Syngas can then be
manufactured into a wide range of hydrocarbon products through
processes such as the Fischer-Tropsch synthesis (discussed below)
to form liquid fuels including methanol, ethanol, diesel, and
gasoline. The result is a powerful technique to not only remove
CO.sub.2 emissions but also create a new alternative source for
fuels that are not derived from petroleum crude oil. The CDR
reaction with methane is exemplified in reaction scheme (11).
CO.sub.2+CH.sub.4.fwdarw.2CO+2H.sub.2 (11)
[0532] Unfortunately, no established industrial technology for CDR
exists today in spite of its tremendous potential value. While not
wishing to be bound by theory, it is thought that the primary
problem with CDR is due to side-reactions from catalyst
deactiviation induced by carbon deposition via the Boudouard
reaction (reaction scheme (12)) and/or methane cracking (reaction
scheme (13)) resulting from the high temperature reaction
conditions. The occurrence of the coking effect is intimately
related to the complex reaction mechanism, and the associated
reaction kinetics of the catalysts employed in the reaction.
2CO.fwdarw.C+CO.sub.2 (12)
CH.sub.4.fwdarw.C+2H.sub.2 (13)
[0533] While not wishing to be bound by theory, the CDR reaction is
thought to proceed through a multistep surface reaction mechanism.
FIG. 9 schematically depicts a CDR reaction 700, in which
activation and dissociation of CH.sub.4 occurs on the metal
catalyst surface 710 to form intermediate "M-C". At the same time,
absorption and activation of CO.sub.2 takes place at the oxide
support surface 720 to provide intermediate "S--CO.sub.2", since
the carbon in a CO.sub.2 molecule as a Lewis acid tends to react
with the Lewis base center of an oxide. The final step is the
reaction between the M-C species and the activated S--CO.sub.2 to
form CO.
[0534] In one embodiment, the present disclosure provides
nanowires, for example the exemplary nanowires disclosed herein,
which are useful as catalysts for the carbon dioxide reforming of
methane. For example, in one embodiment the nanowires are useful as
catalysts in a CDR reaction for the production of syn gas.
[0535] Improvements to the yield, selectivity, and/or conversion in
the CDR reaction employing bulk catalysts are needed. Accordingly,
in one embodiment, the nanowires posses a catalytic activity in the
CDR reaction such that the yield, selectivity, and/or conversion is
better than when the CDR reaction is catalyzed by a corresponding
bulk catalyst. In one embodiment, the disclosure provides a
nanowire having a catalytic activity such that the conversion of
CO.sub.2 to CO in the CDR reaction is greater than at least 1.1
times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times
the conversion of CO.sub.2 to CO compared to the same reaction
under the same conditions but performed with a catalyst prepared
from bulk material having the same chemical composition as the
nanowire. In other embodiments, the conversion of CO.sub.2 to CO in
a CDR reaction catalyzed by the nanowire is greater than 10%,
greater than 20%, greater than 30%, greater than 50%, greater than
75%, or greater than 90%.
[0536] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the yield of CO in a CDR
reaction is greater than at least 1.1 times, 1.25 times, 1.50
times, 2.0 times, 3.0 times, or 4.0 times the yield of CO compared
to the same reaction under the same conditions but performed with a
catalyst prepared from bulk material having the same chemical
composition as the nanowire. In some embodiments the yield of CO in
a CDR reaction catalyzed by the nanowire is greater than 10%,
greater than 20%, greater than 30%, greater than 50%, greater than
75%, or greater than 90%.
[0537] In another embodiment, the disclosure provides a nanowire
having a catalytic activity in a CDR reaction such that the
nanowire has the same or better catalytic activity, but at a lower
temperature, compared a catalyst prepared from bulk material having
the same chemical composition as the nanowire. In some embodiments
the catalytic activity of the nanowires in a CDR reaction is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 20.degree. C. less. In
some embodiments the catalytic activity of the nanowires in a CDR
reaction is the same or better than the catalytic activity of a
catalyst prepared from bulk material having the same chemical
composition as the nanowire, but at a temperature of at least
50.degree. C. less. In some embodiments the catalytic activity of
the nanowires in a CDR reaction is the same or better than the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 100.degree. C. less. In some embodiments the catalytic
activity of the nanowires in a CDR reaction is the same or better
than the catalytic activity of a catalyst prepared from bulk
material having the same chemical composition as the nanowire, but
at a temperature of at least 200.degree. C. less.
[0538] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the selectivity for CO in a
CDR reaction is greater than at least 1.1 times, 1.25 times, 1.50
times, 2.0 times, 3.0 times, or 4.0 times the selectivity for CO
compared to the same reaction under the same conditions but
performed with a catalyst prepared from bulk material having the
same chemical composition as the nanowire. In other embodiments,
the selectivity for CO in a CDR reaction catalyzed by the nanowire
is greater than 10%, greater than 20%, greater than 30%, greater
than 50%, greater than 75%, or greater than 90%.
[0539] In one embodiment, the nanowires disclosed herein enable
efficient conversion of CO.sub.2 to CO in the CDR reaction at
temperatures less than when the corresponding bulk material is used
as a catalyst. For example, in one embodiment, the nanowires enable
efficient conversion (i.e., high yield, conversion, and/or
selectivity) of CO.sub.2 to CO at temperatures of less than
900.degree. C., less than 800.degree. C., less than 700.degree. C.,
less than 600.degree. C., or less than 500.degree. C.
[0540] 4. Fischer-Tropsch Synthesis
[0541] Fischer-Tropsch synthesis (FTS) is a valuable process for
converting synthesis gas (i.e., CO and H.sub.2) into valuable
hydrocarbon fuels, for example, light alkenes, gasoline, diesel
fuel, etc. FTS has the potential to reduce the current reliance on
the petroleum reserve and take advantage of the abundance of coal
and natural gas reserves. Current FTS processes suffer from poor
yield, selectivity, conversion, catalyst deactivation, poor thermal
efficiency and other related disadvantages. Production of alkanes
via FTS is shown in reaction scheme (14), wherein n is an
integer.
CO+2H.sub.2.fwdarw.(1/n)(C.sub.nH.sub.2n)+H.sub.2O (14)
[0542] In one embodiment, nanowires are provided which are useful
as catalysts in FTS processes. For example, in one embodiment the
nanowires are useful as catalysts in a FTS process for the
production of alkanes.
[0543] Improvements to the yield, selectivity, and/or conversion in
FTS processes employing bulk catalysts are needed. Accordingly, in
one embodiment, the nanowires posses a catalytic activity in an FTS
process such that the yield, selectivity, and/or conversion is
better than when the FTS process is catalyzed by a corresponding
bulk catalyst. In one embodiment, the disclosure provides a
nanowire having a catalytic activity such that the conversion of CO
to alkane in an FTS process is greater than at least 1.1 times,
1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the
conversion of CO to alkane compared to the same reaction under the
same conditions but performed with a catalyst prepared from bulk
material having the same chemical composition as the nanowire. In
other embodiments, the conversion of CO to alkane in an FTS process
catalyzed by the nanowire is greater than 10%, greater than 20%,
greater than 30%, greater than 50%, greater than 75%, or greater
than 90%.
[0544] In another embodiment, the disclosure provides a nanowire
having a catalytic activity in an FTS process such that the
nanowire has the same or better catalytic activity, but at a lower
temperature, compared a catalyst prepared from bulk material having
the same chemical composition as the nanowire. In some embodiments
the catalytic activity of the nanowires in an FTS process is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 20.degree. C. less. In
some embodiments the catalytic activity of the nanowires in an FTS
process is the same or better than the catalytic activity of a
catalyst prepared from bulk material having the same chemical
composition as the nanowire, but at a temperature of at least
50.degree. C. less. In some embodiments the catalytic activity of
the nanowires in an FTS process is the same or better than the
catalytic activity of a catalyst prepared from bulk material having
the same chemical composition as the nanowire, but at a temperature
of at least 100.degree. C. less. In some embodiments the catalytic
activity of the nanowires in an FTS process is the same or better
than the catalytic activity of a catalyst prepared from bulk
material having the same chemical composition as the nanowire, but
at a temperature of at least 200.degree. C. less.
[0545] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the yield of alkane in a FTS
process is greater than at least 1.1 times, 1.25 times, 1.50 times,
2.0 times, 3.0 times, or 4.0 times the yield of alkane compared to
the same reaction under the same conditions but performed with a
catalyst prepared from bulk material having the same chemical
composition as the nanowire. In some embodiments the yield of
alkane in an FTS process catalyzed by the nanowire is greater than
10%, greater than 20%, greater than 30%, greater than 50%, greater
than 75%, or greater than 90%.
[0546] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the selectivity for alkanes
in an FTS process is greater than at least 1.1 times, 1.25 times,
1.50 times, 2.0 times, 3.0 times, or 4.0 times the selectivity for
alkanes compared to the same reaction under the same conditions but
performed with a catalyst prepared from bulk material having the
same chemical composition as the nanowire. In other embodiments,
the selectivity for alkanes in an FTS process catalyzed by the
nanowire is greater than 10%, greater than 20%, greater than 30%,
greater than 50%, greater than 75%, or greater than 90%.
[0547] In one embodiment, the nanowires disclosed herein enable
efficient conversion of CO to alkanes in a CDR process at
temperatures less than when the corresponding bulk material is used
as a catalyst. For example, in one embodiment, the nanowires enable
efficient conversion (i.e., high yield, conversion, and/or
selectivity) of CO to alkanes at temperatures of less than
400.degree. C., less than 300.degree. C., less than 250.degree. C.,
less than 200.degree. C., less the 150.degree. C., less than
100.degree. C. or less than 50.degree. C.
[0548] 5. Oxidation of CO
[0549] Carbon monoxide (CO) is a toxic gas and can convert
hemoglobin to carboxyhemoglobin resulting in asphyxiation.
Dangerous levels of CO can be reduced by oxidation of CO to
CO.sub.2 as shown in reaction scheme 15:
CO+1/2O.sub.2.fwdarw.CO.sub.2 (15)
[0550] Catalysts for the conversion of CO into CO.sub.2 have been
developed but improvements to the known catalysts are needed.
Accordingly in one embodiment, the present disclosure provides
nanowires useful as catalysts for the oxidation of CO to
CO.sub.2.
[0551] In one embodiment, the nanowires posses a catalytic activity
in a process for the conversion of CO into CO.sub.2 such that the
yield, selectivity, and/or conversion is better than when the
oxidation of CO into CO.sub.2 is catalyzed by a corresponding bulk
catalyst. In one embodiment, the disclosure provides a nanowire
having a catalytic activity such that the conversion of CO to
CO.sub.2 is greater than at least 1.1 times, 1.25 times, 1.50
times, 2.0 times, 3.0 times, or 4.0 times the conversion of CO to
CO.sub.2 compared to the same reaction under the same conditions
but performed with a catalyst prepared from bulk material and
having the same chemical composition as the nanowire. In other
embodiments, the conversion of CO to CO.sub.2 catalyzed by the
nanowire is greater than 10%, greater than 20%, greater than 30%,
greater than 50%, greater than 75%, or greater than 90%.
[0552] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the yield of CO.sub.2 from
the oxidation of CO is greater than at least 1.1 times, 1.25 times,
1.50 times, 2.0 times, 3.0 times, or 4.0 times the yield of
CO.sub.2 compared to the same reaction under the same conditions
but performed with a catalyst prepared from bulk material having
the same chemical composition as the nanowire. In some embodiments
the yield of CO.sub.2 from the oxidation of CO catalyzed by the
nanowire is greater than 10%, greater than 20%, greater than 30%,
greater than 50%, greater than 75%, or greater than 90%.
[0553] In another embodiment, the disclosure provides a nanowire
having a catalytic activity in an oxidation of CO reaction such
that the nanowire has the same or better catalytic activity, but at
a lower temperature, compared a catalyst prepared from bulk
material having the same chemical composition as the nanowire. In
some embodiments the catalytic activity of the nanowires in an
oxidation of CO reaction is the same or better than the catalytic
activity of a catalyst prepared from bulk material having the same
chemical composition as the nanowire, but at a temperature of at
least 20.degree. C. less. In some embodiments the catalytic
activity of the nanowires in an oxidation of CO reaction is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 50.degree. C. less. In
some embodiments the catalytic activity of the nanowires in an
oxidation of CO reaction is the same or better than the catalytic
activity of a catalyst prepared from bulk material having the same
chemical composition as the nanowire, but at a temperature of at
least 100.degree. C. less. In some embodiments the catalytic
activity of the nanowires in an oxidation of CO reaction is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 200.degree. C. less.
[0554] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the selectivity for CO.sub.2
in the oxidation of CO is greater than at least 1.1 times, 1.25
times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the
selectivity for CO.sub.2 compared to the same reaction under the
same conditions but performed with a catalyst prepared from bulk
material having the same chemical composition as the nanowire. In
other embodiments, the selectivity for CO.sub.2 in the oxidation of
CO catalyzed by the nanowire is greater than 10%, greater than 20%,
greater than 30%, greater than 50%, greater than 75%, or greater
than 90%.
[0555] In one embodiment, the nanowires disclosed herein enable
efficient conversion of CO to CO.sub.2 at temperatures less than
when the corresponding bulk material is used as a catalyst. For
example, in one embodiment, the nanowires enable efficient
conversion (i.e., high yield, conversion, and/or selectivity) of CO
to CO.sub.2 at temperatures of less than 500.degree. C., less than
400.degree. C., less than 300.degree. C., less than 200.degree. C.,
less than 100.degree. C., less than 50.degree. C. or less than
20.degree. C.
[0556] Although various reactions have been described in detail,
the disclosed nanowires are useful as catalysts in a variety of
other reactions. In general, the disclosed nanowires find utility
in any reaction utilizing a heterogeneous catalyst and have a
catalytic activity such that the yield, conversion, and/or
selectivity in reaction catalyzed by the nanowires is better than
the yield, conversion and/or selectivity in the same reaction
catalyzed by a corresponding bulk catalyst.
[0557] 6. Combustion of Hydrocarbons
[0558] In another embodiment, the present disclosure provides a
nanowire having catalytic activity in a reaction for the catalyzed
combustion of hydrocarbons. Such catalytic reactions find utility
in catalytic converters for automobiles, for example by removal of
unburned hydrocarbons in the exhaust by catalytic combustion or
oxidation of soot captured on catalyzed particle filters resulting
in reduction on diesel emissions from the engine. When running
"cold", the exhausts temperature of a diesel engine is quite low,
thus a low temperature catalyst, such as the disclosed nanowires,
is needed to efficiently eliminate all unburned hydrocarbons. In
addition, in case of soot removal on catalyzed particulate filters,
intimate contact between the soot and the catalyst is require; the
open mesh morphology of nanowire catalyst coating is advandageous
to promote such intimate contact between soot and oxidation
catalyst.
[0559] In contrast to a corresponding bulk catalyst, Applicants
have found that certain nanowires, for example the exemplary
nanowires disclosed herein, posses a catalytic activity (for
example because of their morphology) in the combustion of
hydrocarbons such that the yield, selectivity, and/or conversion is
better than when the combustion of hydrocarbons is catalyzed by a
corresponding bulk catalyst. In one embodiment, the disclosure
provides a nanowire having a catalytic activity such that the
combustion of hydrocarbons or soot is greater than at least 1.1
times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times
the combustion of hydrocarbons or soot compared to the same
reaction under the same conditions but performed with a catalyst
prepared from bulk material having the same chemical composition as
the nanowire. In other embodiments, the total combustion of
hydrocarbons or soot catalyzed by the nanowire is greater than 10%,
greater than 20%, greater than 30%, greater than 50%, greater than
75%, or greater than 90%.
[0560] In another embodiment, the disclosure provides a nanowire
having a catalytic activity such that the yield of combusted
hydrocarbon products is greater than at least 1.1 times, 1.25
times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the yield of
combusted hydrocarbon products compared to the same reaction under
the same conditions but performed with a catalyst prepared from
bulk material having the same chemical composition as the nanowire.
In some embodiments the yield of combusted hydrocarbon products in
a reaction catalyzed by the nanowire is greater than 10%, greater
than 20%, greater than 30%, greater than 50%, greater than 75%, or
greater than 90%.
[0561] The stability of the nanowires is defined as the length of
time a catalyst will maintain its catalytic performance without a
significant decrease in performance (e.g., a decrease >20%,
>15%, >10%, >5%, or greater than 1% in hydrocarbon or soot
combustion activity). In some embodiments, the nanowires have
stability under conditions required for the hydrocarbon combustion
reaction of >1 hr, >5 hrs, >10 hrs, >20 hrs, >50
hrs, >80 hrs, >90 hrs, >100 hrs, >150 hrs, >200 hrs,
>250 hrs, >300 hrs, >350 hrs, >400 hrs, >450 hrs,
>500 hrs, >550 hrs, >600 hrs, >650 hrs, >700 hrs,
>750 hrs, >800 hrs, >850 hrs, >900 hrs, >950 hrs,
>1,000 hrs, >2,000 hrs, >3,000 hrs, >4,000 hrs,
>5,000 hrs, >6,000 hrs, >7,000 hrs, >8,000 hrs,
>9,000 hrs, >10,000 hrs, >11,000 hrs, >12,000 hrs,
>13,000 hrs, >14,000 hrs, >15,000 hrs, >16,000 hrs,
>17,000 hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs,
>1 yrs, >2 yrs, >3 yrs, >4 yrs or >5 yrs.
[0562] In another embodiment, the disclosure provides a nanowire
having a catalytic activity in the combustion of hydrocarbons such
that the nanowire has the same or better catalytic activity, but at
a lower temperature, compared a catalyst prepared from bulk
material having the same chemical composition as the nanowire. In
some embodiments the catalytic activity of the nanowires in the
combustion of hydrocarbons is the same or better than the catalytic
activity of a catalyst prepared from bulk material having the same
chemical composition as the nanowire, but at a temperature of at
least 20.degree. C. less. In some embodiments the catalytic
activity of the nanowires in the combustion of hydrocarbons is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 50.degree. C. less. In
some embodiments the catalytic activity of the nanowires in the
combustion of hydrocarbons is the same or better than the catalytic
activity of a catalyst prepared from bulk material having the same
chemical composition as the nanowire, but at a temperature of at
least 100.degree. C. less. In some embodiments the catalytic
activity of the nanowires in the combustion of hydrocarbons is the
same or better than the catalytic activity of a catalyst prepared
from bulk material having the same chemical composition as the
nanowire, but at a temperature of at least 200.degree. C. less.
[0563] 7. Evaluation of Catalytic Properties
[0564] To evaluate the catalytic properties of the nanowires in a
given reaction, for example those reactions discussed above,
various methods can be employed to collect and process data
including measurements of the kinetics and amounts of reactants
consumed and the products formed. In addition to allowing for the
evaluation of the catalytic performances, the data can also aid in
designing large scale reactors, experimentally validating models
and optimizing the catalytic process.
[0565] One exemplary methodology for collecting and processing data
is depicted in FIG. 10. Three main steps are involved. The first
step (block 750) comprises the selection of a reaction and
catalyst. This influences the choice of reactor and how it is
operated, including batch, flow, etc. (block 754). Thereafter, the
data of the reaction are compiled and analyzed (block 760) to
provide insights to the mechanism, rates and process optimization
of the catalytic reaction. In addition, the data provide useful
feedbacks for further design modifications of the reaction
conditions. Additional methods for evaluating catalytic performance
in the laboratory and industrial settings are described in, for
example, Bartholomew, C. H. et al. Fundamentals of Industrial
Catalytic Processes, Wiley-AlChE; 2Ed (1998).
[0566] As an example, in a laboratory setting, an Altamira Benchcat
200 can be employed using a 4 mm ID diameter quartz tube with a 0.5
mm ID capillary downstream. Quartz tubes with 2 mm or 6 mm ID can
also be used. Nanowires are tested in a number of different
dilutions and amounts. In some embodiments, the range of testing is
between 10 and 300 mg. In some embodiments, the nanowires are
diluted with a non-reactive diluent. This diluent can be quartz
(SiO.sub.2) or other inorganic materials, which are known to be
inert in the reaction condition. The purpose of the diluent is to
minimize hot spots and provide an appropriate loading into the
reactor. In addition, the catalyst can be blended with less
catalytically active components as described in more detail
above.
[0567] In a typical procedure, 50 mg is the total charge of
nanowire, optionally including diluent. On either side of the
nanowires a small plug of glass wool is loaded to keep the
nanowires in place. A thermocouple is placed on the inlet side of
the nanowire bed into the glass wool to get the temperature in the
reaction zone. Another thermocouple can be placed on the downstream
end of the nanowire bed into the catalyst bed itself to measure the
exotherms, if any.
[0568] When blending the pure nanowire with diluent, the following
exemplary procedure may be used: x (usually 10-50) mg of the
catalyst (either bulk or test nanowire catalyst) is blended with
(100-x) mg of diluent. Thereafter, about 2 ml of ethanol or water
is added to form a slurry mixture, which is then sonicated for
about 10 minutes. The slurry is then dried in an oven at about
100-140.degree. C. for 2 hours to remove solvent. The resulting
solid mixture is then scraped out and loaded into the reactor
between the plugs of quartz wool.
[0569] Once loaded into the reactor, the reactor is inserted into
the Altamira instrument and furnace and then a temperature and flow
program is started. In some embodiment, the total flow is 50 to 100
sccm of gases but this can be varied and programmed with time. In
one embodiment, the temperatures range from 450.degree. C. to
900.degree. C. The reactant gases comprise air or oxygen (diluted
with nitrogen or argon) and methane in the case of the OCM reaction
and gas mixtures comprising ethane and/or propane with oxygen for
oxidative dehydrogenation (ODH) reactions. Other gas mixtures can
be used for other reactions.
[0570] The primary analysis of these oxidation catalysis runs is
the Gas Chromatography (GC) analysis of the feed and effluent
gases. From these analyses, the conversion of the oxygen and alkane
feed gases can easily be attained and estimates of yields and
selectivities of the products and by-products can be
determined.
[0571] The GC method developed for these experiments employs 4
columns and 2 detectors and a complex valve switching system to
optimize the analysis. Specifically, a flame ionization detector
(FID) is used for the analysis of the hydrocarbons only. It is a
highly sensitive detector that produces accurate and repeatable
analysis of methane, ethane, ethylene, propane, propylene and all
other simple alkanes and alkenes up to five carbons in length and
down to ppm levels.
[0572] There are two columns in series to perform this analysis,
the first is a stripper column (alumina) which traps polar
materials (including the water by-product and any oxygenates
generated) until back-flushed later in the cycle. The second column
associated with the FID is a capillary alumina column known as a
PLOT column, which performs the actual separation of the light
hydrocarbons. The water and oxygenates are not analyzed in this
method.
[0573] For the analysis of the light non-hydrocarbon gases, a
Thermal Conductivity Detector (TCD) may be employed which also
employees two columns to accomplish its analysis. The target
molecules for this analysis are CO.sub.2, ethylene, ethane,
hydrogen, oxygen, nitrogen, methane and CO. The two columns used
here are a porous polymer column known as the Hayes Sep N, which
performs some of the separation for the CO.sub.2, ethylene and
ethane. The second column is a molecular sieve column, which uses
size differentiation to perform the separation. It is responsible
for the separation of H.sub.2, O.sub.2, N.sub.2, methane and
CO.
[0574] There is a sophisticated and timing sensitive switching
between these two columns in the method. In the first 2 minutes or
so, the two columns are operating in series but at about 2 minutes,
the molecular sieve column is by-passed and the separation of the
first 3 components is completed. At about 5-7 minutes, the columns
are then placed back in series and the light gases come off of the
sieve according to their molecular size.
[0575] The end result is an accurate analysis of all of the
aforementioned components from these fixed-bed, gas phase
reactions. Analysis of other reactions and gases not specifically
described above can be performed in a similar manner.
[0576] 8. Downstream Products
[0577] As noted above, in one embodiment the present disclosure is
directed to nanowires useful as catalysts in reactions for the
preparation of a number of valuable hydrocarbon compounds. For
example, in one embodiment the nanowires are useful as catalysts
for the preparation of ethylene from methane via the OCM reaction.
In another embodiment, the nanowires are useful as catalysts for
the preparation of ethylene or propylene via oxidative
dehydrogenation of ethane or propane, respectively. Ethylene and
propylene are valuable compounds, which can be converted into a
variety of consumer products. For example, as shown in FIG. 11,
ethylene can be converted into many various compounds including low
density polyethylene, high density polyethylene, ethylene
dichloride, ethylene oxide, ethylbenzene, linear alcohols, vinyl
acetate, alkanes, alpha olefins, various hydrocarbon-based fuels,
ethanol and the like. These compounds can then be further processed
using methods well known to one of ordinary skill in the art to
obtain other valuable chemicals and consumer products (e.g. the
downstream products shown in FIG. 11). Propylene can be analogously
converted into various compounds and consumer goods including
polypropylenes, propylene oxides, propanol, and the like.
[0578] Accordingly, in one embodiment the disclosure provides a
method of preparing the downstream products of ethylene noted in
FIG. 11. The method comprises converting ethylene into a downstream
product of ethylene, wherein the ethylene has been prepared via a
catalytic reaction employing a nanowire, for example any of the
nanowires disclosed herein. In another embodiment the disclosure
provides a method of preparing low density polyethylene, high
density polyethylene, ethylene dichloride, ethylene oxide,
ethylbenzene, ethanol or vinyl acetate from ethylene, wherein the
ethylene has been prepared as described above.
[0579] In another embodiment, the disclosure provides a method of
preparing a product comprising low density polyethylene, high
density polyethylene, ethylene dichloride, ethylene oxide,
ethylbenzene, ethanol or vinyl acetate, alkenes, alkanes,
aromatics, alcohols, or mixtures thereof. The method comprises
converting ethylene into low density polyethylene, high density
polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene,
ethanol or vinyl acetate, wherein the ethylene has been prepared
via a catalytic reaction employing a nanowires, for example any of
the exemplary nanowires disclosed herein.
[0580] In more specific embodiments of any of the above methods,
the ethylene is produced via an OCM or ODH reaction or combinations
thereof.
[0581] In one particular embodiment, the disclosure provides a
method of preparing a downstream product of ethylene and/or ethane,
wherein the downstream product is a hydrocarbon fuel. For example,
the downstream product of ethylene may be a C.sub.4-C.sub.14
hydrocarbon, including alkanes, alkenes and aromatics. Some
specific examples include 1-butene, 1-hexene, 1-octene, xylenes and
the like. The method comprises converting methane into ethylene,
ethane or combinations thereof by use of a catalytic nanowire, for
example any of the catalytic nanowires disclosed herein, and
further oligomerizing the ethylene and/or ethane to prepare a
downstream product of ethylene and/or ethane. For example, the
methane may be converted to ethylene, ethane or combinations
thereof via the OCM reaction as discussed above. The catalytic
nanowire may be any nanowire and is not limited with respect to
morphology or composition. The catalytic nanowire may be an
inorganic catalytic polycrystalline nanowire, the nanowire having a
ratio of effective length to actual length of less than one and an
aspect ratio of greater than ten as measured by TEM in bright field
mode at 5 keV, wherein the nanowire comprises one or more elements
from any of Groups 1 through 7, lanthanides, actinides or
combinations thereof. Alternatively, the catalytic nanowire may be
an inorganic nanowire comprising one or more metal elements from
any of Groups 1 through 7, lanthanides, actinides or combinations
thereof and a dopant comprising a metal element, a semi-metal
element, a non-metal element or combinations thereof. The nanowires
may additionally comprise any number of doping elements as
discussed above.
[0582] As depicted in FIG. 21, the method begins with charging
methane (e.g., as a component in natural gas) into an OCM reactor.
The OCM reaction may then be performed utilizing a nanowire under
any variety of conditions. Water and CO.sub.2 are optionally
removed from the effluent and unreacted methane is recirculated to
the OCM reactor.
[0583] Ethylene is recovered and charged to an oligomerization
reactor. Optionally the ethylene stream may contain CO.sub.2,
H.sub.2O, N.sub.2, ethane, C3's and/or higher hydrocarbons.
Oligomerization to higher hydrocarbons (e.g., C.sub.4-C.sub.14)
then proceeds under any number of conditions known to those of
skill in the art. For example oligomerization may be effected by
use of any number of catalysts known to those skilled in the art.
Examples of such catalysts include catalytic zeolites, crystalline
borosilicate molecular sieves, homogeneous metal halide catalysts,
Cr catalysts with pyrrole ligands or other catalysts. Exemplary
methods for the conversion of ethylene into higher hydrocarbon
products are disclosed in the following references: Catalysis
Science & Technology (2011), 1(1), 69-75; Coordination
Chemistry Reviews (2011), 255(7-8), 861-880; Eur. Pat. Appl.
(2011), EP 2287142 A1 20110223; Organometallics (2011), 30(5),
935-941; Designed Monomers and Polymers (2011), 14(1), 1-23;
Journal of Organometallic Chemistry 689 (2004) 3641-3668;
Chemistry--A European Journal (2010), 16(26), 7670-7676; Acc. Chem.
Res. 2005, 38, 784-793; Journal of Organometallic Chemistry, 695
(10-11): 1541-1549 May 15, 2010; Catalysis Today Volume 6, Issue 3,
January 1990, Pages 329-349; U.S. Pat. No. 5,968,866; U.S. Pat. No.
6,800,702; U.S. Pat. No. 6,521,806; U.S. Pat. No. 7,829,749; U.S.
Pat. No. 7,867,938; U.S. Pat. No. 7,910,670; U.S. Pat. No.
7,414,006 and Chem. Commun., 2002, 858-859, each of which are
hereby incorporated in their entirety by reference.
[0584] In certain embodiments, the exemplary OCM and
oligomerization modules depicted in FIG. 21 may be adapted to be at
the site of natural gas production, for example a natural gas
field. Thus the natural gas can be efficiently converted to more
valuable and readily transportable hydrocarbon commodities without
the need for transport of the natural gas to a processing
facility.
[0585] Referring to FIG. 21, "natural gasoline" refers to a mixture
of oligomerized ethylene products. The mixture may comprise
1-hexene, 1-octene, linear, branched or cyclic alkanes of 6 or more
hydrocarbons, linear, branched, or cyclic alkenes of 6 or more
hydrocarbons, aromatics, such as benzene, toluene, dimethyl
benzene, xylenes, napthalene, or other oligomerized ethylene
products and combinations thereof. This mixture finds particular
utility in any number of industrial applications, for example
natural gasoline is used as feedstock in oil refineries, as fuel
blend stock by operators of fuel terminals, as diluents for heavy
oils in oil pipelines and other applications. Other uses for
natural gasoline are well-known to those of skill in the art.
EXAMPLES
Example 1
Pechini Synthesis
[0586] Although any metal salt or combination of metal salts can be
combined and processed using the Pechini method to prepare metal
oxide catalysts, this example uses Ca, Nd, and Sr salts to prepare
a mixed metal oxide OCM catalyst. Equimolar aqueous solutions of
strontium nitrate, neodymium nitrate, and calcium nitrate were
prepared. Aliquots of each solution were mixed together to prepare
a desired formulation of Ca.sub.xNd.sub.ySr.sub.z where x, y and z
each independently represent mole fractions of total metal content
in moles. Representative examples of formulations include, but are
not limited to, Ca.sub.50Nd.sub.30Sr.sub.20,
Ca.sub.52Nd.sub.45Sr.sub.05, Ca.sub.75Nd.sub.22Sr.sub.03, and the
like. A solution of citric acid was added to the metal salt mixture
so that the citric acid mole/metal mole ratio was 3:1. Ethylene
glycol (or any polyfunctional alcohol, for example glycerol or
polyvinyl alcohol) was then added to the citric acid/metal salt
solution so that the ethylene glycol/citric acid mole ratio was
1:1. The solution was stirred at room temperature for 1 h. The
solution was placed in a 130.degree. C. oven for 15 h to remove
water and to promote resin formation. After 15 h, a hard dark resin
was observed. The resin was placed in furnace and heated to
500.degree. C. for 8 h. The remaining material was then heated to
650.degree. C. for 2 h to yield the desired metal oxide
product.
Example 2
Polymer Templated Synthesis
[0587] Dextran is a water-soluble polymer with a wide range of
molecular weights and is a useful templating source. Briefly, a
metal precursor and dextran are dissolved in water to produce a
viscous solution. The solution is dried to make a metal organic
composite and then calcined (oven or microwave) to remove the
dextran template. Optionally, multiple metal precursors are
dissolved in a dextran solution. Mixed metal oxide materials are
readily prepared by dissolving different metal salts, in the
desired ratio, in a viscous dextran solution. The solution is dried
and calcined as described above to yield mixed metal oxide systems
for OCM catalysis. Alternatively, freeze drying may be employed to
dry the dextran/metal solution to prepare a more controllable
porosity in the metal and mixed metal oxide materials.
[0588] Agarose is also used to prepare metal and mixed metal oxides
for OCM catalysts. Agarose readily forms a gel that can be used as
templating source by impregnating the gel with metal precursors. An
agarose gel is impregnated with a metal precursor. Optionally the
wet gel is impregnated with multiple metal precursors at the same
time or step-wise for the eventual preparation of mixed metal oxide
materials.
[0589] In an alternative to the above method, the metal-agarose
composite is treated with a base to precipitate the metal
precursors within the gel framework before calcination. Freeze
drying is optionally used to remove the water from the
metal-agarose composite. The agarose is removed by oven or
microwave calcination to yield metal and mixed metal OCM
catalysts.
[0590] Other catalysts are prepared according to the above methods
employing any of the polymers and metal compositions disclosed
herein.
Example 3
Preparation Mg(OH).sub.2 Nanowires
[0591] FIG. 11 shows a generic reaction scheme for preparing MgO
nanowires (with dopant) via a polymer template. The reaction
container can be anything from a small vial (for milliliter scale
reactions) up to large bottles (for liter reaction scale
reactions).
[0592] A magnesium solution and a base solution are added to the
polymer solution in order to precipitate Mg(OH).sub.2. The
magnesium solution can be of any soluble magnesium salt, e.g.
MgX2.6H2O (X.dbd.Cl, Br, I), Mg(NO.sub.3).sub.2, MgSO.sub.4,
magnesium acetate, etc. The range of the magnesium concentration in
the reaction mixture is quite narrow, typically at 0.01M. The
combination of the polymer concentration and the magnesium
concentration (i.e. the ratio between the polymer and magnesium
ions) can play a part in determining both the nanowires formation
process window and their morphology.
[0593] The base can be any alkali metal hydroxide (e.g. LiOH, NaOH,
KOH), soluble alkaline earth metal hydroxide (e.g. Sr(OH).sub.2,
Ba(OH).sub.2) or any ammonium hydroxide (e.g., NR.sub.4OH, R.dbd.H,
CH.sub.3, C.sub.2H.sub.5, etc.). Certain selection criteria for the
base include: adequate solubility (at least several orders of
magnitude higher than Mg(OH).sub.2 for Mg(OH).sub.2 nanowires),
high enough strength (pH of the reaction mixture should be at least
11) and an inability to coordinate magnesium (for Mg(OH).sub.2
nanowires) to form soluble products. LiOH is a preferred choice for
Mg(OH).sub.2 nanowires formation because lithium may additionally
be incorporated in the Mg(OH).sub.2 as a dopant, providing a Li/MgO
doped catalyst for OCM.
[0594] Another factor concerning the base is the amount of base
used or the concentration ratio of OH.sup.-/Mg.sup.2+, i.e. the
ratio between the number of OH equivalents added and the number of
moles of Mg added. In order to fully convert the Mg ions in
solution to Mg(OH).sub.2, the OH/Mg ratio needed is 2. The
OH.sup.-/Mg.sup.2+ used in the formation of Mg(OH).sub.2 nanowires
ranges from 0.5 to 2 and, depending on this ratio, the morphology
of the reaction product changes from thin nanowires to
agglomerations of nanoparticles. The OH.sup.-/Mg.sup.2+ ratio is
determined by the pH of the reaction mixture, which needs to be at
least 11. If the pH is below 11, no precipitation is observed, i.e.
no Mg(OH).sub.2 is formed. If the pH is above 12, the morphology of
the nanowires begins to change and more nanoparticles are obtained,
i.e. non-selective precipitation.
[0595] Considering the narrow window of magnesium concentration in
which Mg(OH).sub.2 nanowires can be obtained, the other key
synthetic parameters that determine the nanowires formation and
morphology include but are not limited to: polymer type and
concentration thereof, the concentration ratio of
Mg.sup.2+/polymer, the concentration ratio of OH.sup.-/Mg.sup.2+,
the incubation time of polymer and Mg.sup.2+; incubation time of
polymer and the OH.sup.-; the sequence of adding anion and metal
ions; pH; the solution temperature in the incubation step and/or
growth step; the types of metal precursor salt (e.g., MgCl.sub.2 or
Mg(NO.sub.3).sub.2); the types of anion precursor (e.g., NaOH or
LiOH); the number of additions; the time that lapses between the
additions of the metal salt and anion precursor, including, e.g.,
simultaneous (zero lapse) or sequential additions.
[0596] The Mg salt solution and the base are added sequentially,
separated by an incubation time (i.e., the first incubation time).
The sequence of addition has an effect on the morphology of the
nanowires. The first incubation time can be at least 1 h and it
should be longer in the case the magnesium salt solution is added
first. The Mg salt solution and the base can be added in a single
"shot" or in a continuous slow flow using a syringe pump or in
multiple small shots using a liquid dispenser robot. The reaction
is then carried either unstirred or with only mild to moderate
stirring for a specific time (i.e., the second incubation time).
The second incubation time is not as strong a factor in the
synthesis of Mg(OH).sub.2 nanowires, but it should be long enough
for the nanowires to precipitate out of the reaction solution
(e.g., several minutes). For practical reasons, the second
incubation time can be as long as several hours. The reaction
temperature can be anything from just above freezing temperature
(e.g., 4.degree. C.) up to 80.degree. C. The temperature affects
the nanowires morphology.
[0597] The precipitated Mg(OH).sub.2 nanowires are isolated by
centrifuging the reaction mixture and decanting the supernatant.
The precipitated material is then washed at least once with a water
solution with pH>10 to avoid redissolution of the Mg(OH).sub.2
nanowires. Typically, the washing solution used can be ammonium
hydroxide water solution or an alkali metal hydroxide solution
(e.g., LiOH, NaOH, KOH). This mixture is centrifuged and the
supernatant decanted. Finally, the product can be either dried
(see, Example 5) or resuspended in ethanol for TEM analysis.
[0598] FIG. 11 depicts one embodiment for preparing Mg(OH).sub.2
nanowires. In a different embodiment, the order of addition may be
reversed, for example in an exemplary 4 ml scale synthesis of
Mg(OH).sub.2 nanowires and polymer are mixed in a 8 ml vial with
0.02 ml of 1 M LiOH aqueous solution and left incubating overnight
(.about.15 h). 0.04 ml of 1 M MgCl.sub.2 aqueous solution are then
added using a pipette and the mixture is mixed by gentle shaking.
The reaction mixture is left incubating unstirred for 24 h. After
the incubation time, the mixture is centrifuged, and the
supernatant is decanted. The precipitated material is resuspended
in 2 ml of 0.001 M LiOH aqueous solution (pH=11), the mixture is
centrifuged and the supernatant decanted. The obtained Mg(OH).sub.2
nanowires are characterized by TEM as described in Example 4.
Example 4
Characterization of Mg(OH).sub.2 Nanowires
[0599] Mg(OH).sub.2 nanowires prepared according to Example 3 are
characterized by TEM in order to determine their morphology. First,
a few microliters (.about.500) of ethanol is used to suspend the
isolated Mg(OH).sub.2. The nanowires are then deposited on a TEM
grid (copper grid with a very thin carbon layer) placed on filter
paper to help wick out any extra liquid. After allowing the ethanol
to dry, the TEM grid is loaded in a TEM and characterized. TEM is
carried out at 5 KeV in bright field mode in a DeLong LVEM5.
[0600] The nanowires are additionally characterized by XRD (for
phase identification) and TGA (for calcination optimization).
Example 5
Calcination of Mg(OH).sub.2 Nanowires
[0601] The isolated nanowires as prepared in Example 3 are dried in
an oven at relatively low temperature (60-120.degree. C.) prior to
calcination.
[0602] The dried material is placed in a ceramic boat and calcined
in air at 450 C..degree. in order to convert the Mg(OH).sub.2
nanowires into MgO nanowires. The calcination recipe can be varied
considerably. For example, the calcination can be done relatively
quickly like in these two examples: [0603] load in a muffle oven
preheated at 450.degree. C., calcination time=120 min [0604] load
in a muffle oven (or tube furnace) at room temperature and ramp to
450.degree. C. with 5.degree. C./min rate, calcination time=60
min
[0605] Alternatively, the calcination can be done in steps that are
chosen according to the TGA signals like in the following example:
[0606] load in a muffle oven (or tube furnace) at room temperature,
ramp to 100.degree. C. with 2.degree. C./min rate, dwell for 60
min, ramp to 280.degree. C. with 2.degree. C./min rate, dwell for
60 min, ramp to 350.degree. C. with 2.degree. C./min rate, dwell
for 60 min and finally ramp to 450.degree. C. with 2.degree. C./min
rate, dwell for 60 min.
[0607] Generally, a step recipe is preferable since it should allow
for a better, smoother and more complete conversion of Mg(OH).sub.2
into MgO. Optionally, the calcined product is ground into a fine
powder.
Example 6
Preparation of Li Doped MgO Nanowires
[0608] Doping of nanowires is achieved by using the incipient
wetness impregnation method. Before impregnating the MgO nanowires
with the doping solution, the maximum wettability (i.e. the ability
of the nanowires to absorb the doping solution before becoming a
suspension or before "free" liquid is observed) of the nanowires is
determined. This is a very important step for an accurate
absorption of the doping metal on the MgO surface. If too much
dopant solution is added and a suspension is formed, a significant
amount of dopant will crystallize unabsorbed upon drying and if not
enough dopant solution is added, significant portions of the MgO
surface will not be doped.
[0609] In order to determine the maximum wettability of the MgO
nanowires, small portions of water are dropped on the calcined MgO
powder until a suspension is formed, i.e. until "free" liquid is
observed. The maximum wettability is determined to be the total
amount of water added before the suspension forms. The
concentration of the doping solution is then calculated so that the
desired amount of dopant is contained in the volume of doping
solution corresponding to the maximum wettability of the MgO
nanowires. In another way to describe the incipient wetness
impregnation method, the volume of the doping solution is set to be
equal to the pore volume of the nanowires, which can be determined
by BET (Brunauer, Emmett, Teller) measurements. The doping solution
is then drawn into the pores by capillary action.
[0610] In one embodiment, the doping metal for MgO based catalysts
for OCM is lithium (see, also, FIG. 11). Thus, in one embodiment
the dopant source can be any soluble lithium salt as long as it
does not introduce undesired contaminants. Typically, the lithium
salts used are LiNO.sub.3, LiOH or Li.sub.2CO.sub.3. LiNO.sub.3 and
LiOH are preferred because of their higher solubility. In one
embodiment, the lithium content in MgO catalysts for OCM ranges
from 0 to 10 wt % (i.e. about 0 to 56 at %).
[0611] The calculated amount of dopant solution of the desired
concentration is dropped onto the calcined MgO nanowires. The
obtained wet powder is dried in an oven at relatively low
temperature (60-120.degree. C.) and calcined using one of the
recipes described above. It is noted that, during this step, no
phase transition occurs (MgO has already been formed in the
previous calcination step) and thus a step recipe (see previous
paragraph) may not be necessary.
[0612] The dopant impregnation step can also be done prior to the
calcination, after drying the Mg(OH).sub.2 nanowires isolated from
the reaction mixture. In this case, the catalyst can be calcined
immediately after the dopant impregnation, i.e. no drying and
second calcination steps would be required since its goals are
accomplished during the calcination step.
[0613] Three identical syntheses are made in parallel. In each
synthesis, 80 ml of concentrated polymer solution is mixed in a 100
ml glass bottle with 0.4 ml of 1 M LiOH aqueous solution and left
incubating for 1 h. 0.8 ml of 1 M MgCl.sub.2 aqueous solution are
added using a pipette and the mixture is mixed by gently shaking
it. The reaction mixture is left incubating unstirred for 72 h at
60.degree. C. in an oven. After the incubation time, the mixture is
centrifuged. The precipitated material is resuspended in 20 ml of
0.06 M NH.sub.4OH aqueous solution (pH=11), the mixture is
centrifuged and the supernatant decanted. The obtained Mg(OH).sub.2
nanowires are resuspended in ethanol. The ethanol suspensions of
the three identical syntheses are combined and a few microliters of
the ethanol suspension are used for TEM analysis. The ethanol
suspension is centrifuged and the supernatant decanted. The
gel-like product is transferred in a ceramic boat and dried for 1 h
at 120.degree. C. in a vacuum oven.
[0614] The dried product is calcined in a tube furnace using a step
recipe (load in the furnace at room temperature, ramp to
100.degree. C. with 2.degree. C./min rate, dwell for 60 min, ramp
to 280.degree. C. with 2.degree. C./min rate, dwell for 60 min,
ramp to 350.degree. C. with 2.degree. C./min rate, dwell for 60
min, ramp to 450.degree. C. with 2.degree. C./min rate, dwell for
60 min and finally cool to room temperature). The calcined product
is ground to a fine powder.
[0615] 10 mg of the calcined product are impregnated with a LiOH
aqueous solution. First, the maximum wettability is determined by
adding water to the calcined product in a ceramic boat until the
powder is saturated but no "free" liquid was observed. The maximum
expected wettability is about 12 .mu.l. Since the target doping
level is 1 wt % lithium, the necessary concentration of the LiOH
aqueous solution is calculated to be 1.2 M. The calcined product is
dried again for 1 h at 120.degree. C. to remove the water used to
determine the wettability of the powder. 12 .mu.l of the 1.2 M LiOH
solution are dropped on the MgO nanowires powder. The wet powder is
dried for 1 h at 120.degree. C. in a vacuum oven and finally
calcined in a muffle oven (load at room temperature, ramp to
460.degree. C. with 2.degree. C./min ramp, dwell for 120 min).
Example 7
OCM Catalyzed by La.sub.2O.sub.3 Nanowires
[0616] A 20 mg sample of a polymer-based Sr (5%) doped
La.sub.2O.sub.3 catalyst is diluted with 80 mg of quartz sand and
placed into a reactor (run WPS21). The gas flows are held constant
at 9 sccm methane, 3 sccm oxygen and 6 sccm of argon. The upstream
temperature (just above the bed) is varied from 500.degree. C. to
800.degree. C. in 100.degree. C. increments and then decreased back
down to 600.degree. C. in 50.degree. C. increments. The vent gas
analysis is gathered at each temperature level.
[0617] The polymer-based nanowires according to the present
disclosure are expected to comprise better OCM activity (i.e.,
conversion of methane, C2 selectivity, yield, etc.) compared to a
corresponding bulk catalyst.
Example 8
Oxidative Dehydrogenation Catalyzed by MgO Nanowires
[0618] A 10 mg sample of polymer-based Li doped MgO catalyst is
diluted with 90 mg of quartz sand and placed in a reactor. The gas
flows are held constant at 8 sccm alkane mix, 2 sccm oxygen and 10
sccm of argon. The upstream temperature (just above the bed) is
varied from 500.degree. C. to 750.degree. C. in 50-100.degree. C.
increments. The vent gas analysis is gathered at each temperature
level.
[0619] The polymer-based nanowires according to the present
disclosure are expected to comprise better conversion of ethane and
propane compared to a corresponding bulk catalyst.
Example 9
Preparation of Sr Doped La.sub.2O.sub.3 Nanowires
[0620] Sr doped La.sub.2O.sub.3 nanowires are prepared according to
the following method.
[0621] A 57 mg aliquot of La.sub.2O.sub.3 nanowires prepared as
described herein is then mixed with 0.174 ml of a 0.1 M solution of
Sr(NO.sub.3).sub.2. This mixture is then stirred on a hot plate at
90.degree. C. until a paste was formed.
[0622] The paste is then dried for 1 h at 120.degree. C. in a
vacuum oven and finally calcined in a muffle oven in air according
to the following procedure: (1) load in the furnace at room
temperature; (2) ramp to 200.degree. C. with 3.degree. C./min rate;
(3) dwell for 120 min; (3) ramp to 400.degree. C. with 3.degree.
C./min rate; (4) dwell for 120 min; (5) ramp to 500.degree. C. with
3.degree. C./min rate; and (6) dwell for 120 min. The calcined
product is then ground to a fine powder.
Example 10
Preparation of La.sub.2O.sub.3 Nanowires
[0623] Two identical syntheses are made in parallel. In each
synthesis, 360 ml of polymer solution are mixed in a 500 ml plastic
bottle with 1.6 ml of 0.1 M LaCl.sub.3 aqueous solution and left
incubating for at least 1 hour. After this incubation period, a
slow multistep addition is conducted with 20 ml of 0.1 M LaCl3
solution and 40 ml of 0.3 M NH4OH. This addition is conducted in 24
hours and 100 steps. The reaction mixture is left stirred for at
least another hour at room temperature. After that time the
suspension is centrifuged in order to separate the solid phase from
the liquid phase. The precipitated material is then re-suspended in
25 ml of ethanol. The ethanol suspensions from the two identical
syntheses are combined and centrifuged in order to remove
un-reacted species. The gel-like product remaining is then dried
for 15 hours at 65.degree. C. in an oven and then calcined in a
muffle oven in air (load in the furnace at room temperature, ramp
to 100.degree. C. with 2.degree. C./min rate, dwell for 30 min,
ramp to 400.degree. C. with 2.degree. C./min rate, dwell for 240
min, ramp to 550.degree. C. with 2.degree. C./min rate, dwell for
240 min, cool to room temperature).
Example 11
Preparation of Mg/Na Doped La.sub.2O.sub.3 Nanowires
[0624] Two identical syntheses are made in parallel. In each
synthesis, 360 ml of polymer solution are mixed in a 500 ml plastic
bottle with 1.6 ml of 0.1 M LaCl.sub.3 aqueous solution and left
incubating for at least 1 hour. After this incubation period, a
slow multistep addition is conducted with 20 ml of 0.1 M LaCl.sub.3
solution and 40 ml of 0.3 M NH.sub.4OH. This addition is conducted
in 24 hours and 100 steps. The reaction mixture is left stirred for
at least another hour at room temperature. After that time, the
suspension is centrifuged in order to separate the solid phase from
the liquid phase. The precipitated material is then resuspended in
25 ml of ethanol. The ethanol suspensions from the two identical
syntheses are combined and centrifuged in order to remove
un-reacted species. The gel-like product remaining is then dried
for 15 hours at 65.degree. C. in an oven.
[0625] The target doping level is 20 at % Mg and 5 at % Na at %
refers to atomic percent). 182 mg of the dried product are
suspended in 2.16 ml deionized water, 0.19 ml 1 M
Mg(NO.sub.3).sub.2 aqueous solution and 0.05 ml 1M NaNO.sub.3
aqueous solution. The resulting slurry is stirred at room
temperature for 1 hour, sonicated for 5 min, then dried at
120.degree. C. in and oven until the powder is fully dried and
finally calcined in a muffle oven in air (load in the furnace at
room temperature, ramp to 100.degree. C. with 2.degree. C./min
rate, dwell for 30 min, ramp to 400.degree. C. with 2.degree.
C./min rate, dwell for 60 min, ramp to 550.degree. C. with
2.degree. C./min rate, dwell for 60 min, ramp to 650.degree. C.
with 2.degree. C./min rate, dwell for 60 min, ramp to 750.degree.
C. with 2.degree. C./min rate, dwell for 240 min, cool to room
temperature).
Example 12
Oxidative Coupling of Methane Catalyzed by Mg/Na Doped
La.sub.2O.sub.3 Nanowires
[0626] 50 mg of Mg/Na-doped La.sub.2O.sub.3 nanowires catalyst from
example 12 are placed into a reactor tube (4 mm ID diameter quartz
tube with a 0.5 mm ID capillary downstream), which is then tested
in an Altamira Benchcat 203. The gas flows are held constant at 46
sccm methane and 54 sccm air, which correspond to a
CH.sub.4/O.sub.2 ratio of 4 and a feed gas-hour space velocity
(GHSV) of about 130000/hour. The reactor temperature is varied from
400.degree. C. to 450.degree. C. in a 50.degree. C. increment, from
450.degree. C. to 550.degree. C. in 25.degree. C. increments and
from 550.degree. C. to 750.degree. C. in 50.degree. C. increments.
The vent gases are analyzed with gas chromatography (GC) at each
temperature level.
[0627] In another example, 50 mg of Mg/Na-doped La.sub.2O.sub.3
nanowires catalyst from example 12 are placed into a reactor tube
(4 mm ID diameter quartz tube with a 0.5 mm ID capillary
downstream), which is then tested in an Altamira Benchcat 203. The
gas flows are held constant at 46 sccm methane and 54 sccm air,
which correspond to a feed gas-hour space velocity (GHSV) of about
130000 h.sup.-1. The CH4/O2 ratio is 5.5. The reactor temperature
is varied from 400.degree. C. to 450.degree. C. in a 50.degree. C.
increment, from 450.degree. C. to 550.degree. C. in a 25.degree. C.
increments and from 550.degree. C. to 750.degree. C. in 50.degree.
C. increments. The vent gases are analyzed with gas chromatography
(GC) at each temperature level.
Example 13
Nanowire Synthesis
[0628] Nanowires may be prepared by hydrothermal synthesis from
metal hydroxide gels (made from metal salt+base). In some
embodiments, this method is applicable to lanthanides, for example
La, Nd, Pr, Sm, Eu, and lanthanide containing mixed oxides.
[0629] Alternatively, nanowires can be prepared by synthesis from
metal hydroxide gel (made from metal salt+base) under reflux
conditions. In some embodiments, this method is applicable to
lanthanides, for example La, Nd, Pr, Sm, Eu, and lanthanide
containing mixed oxides.
[0630] Alternatively, the gel can be aged at room temperature.
Certain embodiments of this method are applicable for making
magnesium hydroxychloride nanowires, which can be converted to
magnesium hydroxide nanowires and eventually to MgO nanowires. In a
related method, hydrothermal treatment of the gel instead of aging
is used.
[0631] Nanowires may also be prepared by polyethyleneglycol
assisted hydrothermal synthesis. For example, Mn containing
nanowires may be prepared according to this method using methods
known to those skilled in the art. Alternatively, hydrothermal
synthesis directly from the oxide can be used.
Example 14
Preparation of Nd.sub.2O.sub.3, Eu.sub.2O.sub.3 and Pr.sub.2O.sub.3
Nanowires
[0632] Three syntheses are made in parallel. In each synthesis, 10
ml of polymer solution are mixed in a 60 ml glass vial with 25
.mu.l of 0.08M NdCl.sub.3, EuCl.sub.3 or PrCl.sub.3 aqueous
solutions, respectively and left incubating for at least 1 hour.
After this incubation period, a slow multistep addition is
conducted with 630 .mu.l of 0.08M LaCl.sub.3, EuCl.sub.3 or
PrCl.sub.3 aqueous solutions, respectively and 500 .mu.l of 0.3M
NH4OH. This addition is conducted in 33 hours and 60 steps. The
reaction mixtures are left stirred for at least another 10 hour at
room temperature. After that time the suspensions are centrifuged
in order to separate the solid phase from the liquid phase. The
precipitated material is then re-suspended in 4 ml of ethanol. The
ethanol suspensions are centrifuged in order to finish removing
un-reacted species. The gel-like product remaining is then dried
for 1 hours at 65.degree. C. in an oven and then calcined in a
muffle oven in air (load in the furnace at room temperature, ramp
to 100.degree. C. with 2.degree. C./min rate, dwell for 30 min,
ramp to 500.degree. C. with 2.degree. C./min rate, dwell for 240
min, cool to room temperature). The obtained Nd(OH).sub.3,
Eu(OH).sub.3 and Pr(OH).sub.3 nanowires were characterized by TEM
before being dried.
Example 15
Preparation of Ce.sub.2O.sub.3/La.sub.2O.sub.3 Mixed Oxide
Nanowires
[0633] In this synthesis, 15 ml of polymer are mixed in a 60 ml
glass vial with 15 .mu.l of 0.1 M La(NO.sub.3).sub.3 aqueous
solution and left incubating for about 16 hour. After this
incubation period, a slow multistep addition is conducted with 550
.mu.l of 0.2M Ce(NO.sub.3).sub.3 aqueous solution, 950 .mu.l of
0.2M La(NO.sub.3).sub.3 aqueous solution and 1500 .mu.l of 0.4M
NH.sub.4OH. This addition is conducted in 39 hours and 60 steps.
The reaction mixtures are left stirred for at least another 10
hours at room temperature. After that time the suspensions are
centrifuged in order to separate the solid phase from the liquid
phase. The precipitated material is then re-suspended in 4 ml of
ethanol. The ethanol suspensions are centrifuged in order to finish
removing un-reacted species. The gel-like product remaining is then
dried for 1 hours at 65.degree. C. in an oven and then calcined in
a muffle oven in air (load in the furnace at room temperature, ramp
to 100.degree. C. with 2.degree. C./min rate, dwell for 30 min,
ramp to 500.degree. C. with 2.degree. C./min rate, dwell for 120
min, cool to room temperature).
Example 16
Oligomerization of Ethylene to Liquid Hydrocarbon Fuels with High
Aromatics Content
[0634] 0.1 g of the zeolite ZSM-5 is loaded into a fixed bed
micro-reactor and heated at 400.degree. C. for 2 h under nitrogen
to activate the catalyst. The OCM effluent, containing ethylene and
ethane, is reacted over the catalyst at 400.degree. C. at a flow
rate of 50 mL/min and GSHV=3000-10000 mL/(g h). The reaction
products are separated into liquid and gas components using a cold
trap. The gas and liquid components are analyzed by gas
chromatography. C5-C10 hydrocarbon liquid fractions, such as xylene
and isomers thereof, represent .gtoreq.90% of the liquid product
ratio while the C11-C15 hydrocarbon fraction represents the
remaining 10% of the product ratio.
Example 17
Oligomerization of Ethylene to Liquid Hydrocarbon Fuels with High
Olefins Content
[0635] 0.1 g of the zeolite ZSM-5 doped with nickel is loaded into
a fixed bed micro-reactor and heated at 350.degree. C. for 2 h
under nitrogen to activate the catalyst. The OCM effluent,
containing ethylene and ethane, is reacted over the catalyst at
250-400.degree. C. temperature rage with GSHV=1000-10000 mL/(g h).
The reaction products are separated into liquid and gas components
using a cold trap. The gas and liquid components are analyzed by
gas chromatography. C.sub.4-C.sub.10 olefin hydrocarbon liquid
fractions, such as butene, hexane and octene represent .gtoreq.95%
of the liquid product ratio while the C.sub.12-C.sub.18 hydrocarbon
fraction represents the remaining 5% of the product ratio. Some
trace amounts of odd numbered olefins are also possible in the
product.
Example 18
OCM Catalyzed by La.sub.2O.sub.3 Nanowires
[0636] 50 mg of a nanowire catalyst as described herein are placed
into a reactor tube (4 mm ID diameter quartz tube with a 0.5 mm ID
capillary downstream), which is then tested in an Altamira Benchcat
203. The gas flows are held constant at 46 sccm methane and 54 sccm
air, which correspond to a CH.sub.4/O2 ratio of 4 and a feed
gas-hour space velocity (GHSV) of about 130000/hour. The reactor
temperature is varied from 400.degree. C. to 500.degree. C. in a
100.degree. C. increment and from 500.degree. C. to 850.degree. C.
in 50.degree. C. increments. The vent gases are analyzed with gas
chromatography (GC) at each temperature level.
Example 19
Preparation of Catalytic Material Comprising Cordierite Honeycomb
Ceramic Supported Nd.sub.2O.sub.3 Nanowires
[0637] Nd.sub.2O.sub.3 nanowires are prepared in a manner analogous
to those described herein.
[0638] A 400 mg aliquot of Nd.sub.2O.sub.3 nanowires is mixed with
2 g of DI water and placed into a 5 ml glass vial containing 2 mm
Yttria Stabilized Zirconia milling balls. The vial is placed on a
shaker at 2000 RPM and agitated for 30 minutes. A thick slurry is
obtained.
[0639] A 3/8 inch diameter core is cut along the channel direction
into a 400 CPSI (channel per square inche) cordierite honeycomb
monolith and cut in length so the core volume is approximately 1
ml.
[0640] The core is placed into a 3/8 inch tube, and the catalyst
slurry is fed on top of the ceramic core and pushed with compressed
air through the monolith channel. The excess slurry is captured
into a 20 ml vial. The coated core is removed from the 3/8 inch
tube and placed into a drying oven at 200.degree. C. for 1
hour.
[0641] The coating step is repeated twice more time with the
remaining slurry followed by drying at 200.degree. C. and
calcination at 500.degree. C. for 4 hours. The catalyst amount
deposited on the monolith channel walls is approximately 50 mg and
comprises very good adhesion to the ceramic wall.
Example 20
Preparation of Catalytic Material Comprising Silicon Carbide
Ceramic Foam Supported Nd.sub.2O.sub.3 Nanowires
[0642] Nd.sub.2O.sub.3 nanowires are prepared in a manner analogous
to the above examples.
[0643] A 400 mg aliquot of Nd.sub.2O.sub.3 nanowires is mixed with
2 g of DI water and placed into a 5 ml glass vial containing 2 mm
Yttria Stabilized Zirconia milling balls. The vial is placed on a
shaker at 2000 RPM and agitated for 30 minutes. A thick slurry is
obtained.
[0644] A 3/8 inch diameter core is cut from a 65 PPI (Pore Per
Inch) SiC foam and cut in length so the core volume is
approximately 1 ml.
[0645] The core is placed into a 3/8 inch tube and the catalyst
slurry is fed on top of the ceramic core and pushed with compressed
air through the monolith channel. The excess slurry is captured
into a 20 ml vial. The coated core is removed from the 3/8 inch
tube and placed into a drying oven at 200.degree. C. for 1
hour.
[0646] The coating step is repeated twice more time with the
remaining slurry followed by drying at 200.degree. C. and
calcination at 500.degree. C. for 4 hours. The catalyst amount
deposited on the monolith channel walls is approximately 60 mg and
comprises very good adhesion to the ceramic mesh.
Example 21
Preparation of Catalytic Material Comprising Silicon Carbide and
Nd.sub.2O.sub.3 Nanowires
[0647] Nd.sub.2O.sub.3 nanowires are prepared in a manner analogous
to the above examples
[0648] A 400 mg aliquot of Nd.sub.2O.sub.3 nanowires is dry blend
mixed with 400 mg of 200-250 mesh SiC particles for 10 minutes or
until the mixture appears homogeneous and wire clusters are no
longer visible. The mixture is then placed into a 1/4 inch die and
pressed in 200 mg batches. The pressed pellets are then placed into
an oven and calcined at 600.degree. C. for 2 hours. The crush
strength of the pellet obtained is comparable to the crush strength
of a pellet made with only Nd.sub.2O.sub.3 nanowires.
Example 22
Preparation of Sr Doped La.sub.2O.sub.3 Nanowires
[0649] Sr doped La.sub.2O.sub.3 nanowires are prepared according to
the following method.
[0650] A 57 mg aliquot of La.sub.2O.sub.3 nanowires prepared as
described herein is then mixed with 0.174 ml of a 0.1 M solution of
Sr(NO.sub.3).sub.2. This mixture is then stirred on a hot plate at
90.degree. C. until a paste was formed.
[0651] The paste is then dried for 1 h at 120.degree. C. in a
vacuum oven and finally calcined in a muffle oven in air according
to the following procedure: (1) load in the furnace at room
temperature; (2) ramp to 200.degree. C. with 3.degree. C./min rate;
(3) dwell for 120 min; (3) ramp to 400.degree. C. with 3.degree.
C./min rate; (4) dwell for 120 min; (5) ramp to 500.degree. C. with
3.degree. C./min rate; and (6) dwell for 120 min. The calcined
product is then ground to a fine powder.
[0652] The various embodiments described above can be combined to
provide further embodiments. All of the U.S. patents, U.S. patent
application publications, U.S. patent applications, foreign
patents, foreign patent applications and non-patent publications
referred to in this specification and/or listed in the Application
Data Sheet, are incorporated herein by reference, in their
entirety. Aspects of the embodiments can be modified, if necessary
to employ concepts of the various patents, applications and
publications to provide yet further embodiments. These and other
changes can be made to the embodiments in light of the
above-detailed description. In general, in the following claims,
the terms used should not be construed to limit the claims to the
specific embodiments disclosed in the specification and the claims,
but should be construed to include all possible embodiments along
with the full scope of equivalents to which such claims are
entitled. Accordingly, the claims are not limited by the
disclosure.
* * * * *