U.S. patent number 3,853,739 [Application Number 05/265,690] was granted by the patent office on 1974-12-10 for platinum group metal oxide coated electrodes.
This patent grant is currently assigned to Electronor Corporation. Invention is credited to James M. Kolb, Kevin J. O'Leary.
United States Patent |
3,853,739 |
Kolb , et al. |
December 10, 1974 |
PLATINUM GROUP METAL OXIDE COATED ELECTRODES
Abstract
A dimensionally stable electrode comprises an
electrically-conductive substrate having bound to the surface
thereof a coating which consists essentially of a solid solution of
platinum group oxides. The electrodes are fabricated by applying a
solution of a binder having dispersed therein a preformed
particulate solid solution of the foregoing type.
Inventors: |
Kolb; James M. (Mentor, OH),
O'Leary; Kevin J. (Cleveland Heights, OH) |
Assignee: |
Electronor Corporation (Panama
City, PM)
|
Family
ID: |
23011494 |
Appl.
No.: |
05/265,690 |
Filed: |
June 23, 1972 |
Current U.S.
Class: |
204/290.09 |
Current CPC
Class: |
C25B
11/093 (20210101) |
Current International
Class: |
C25B
11/00 (20060101); C25B 11/04 (20060101); B01k
003/06 (); C01b 007/06 () |
Field of
Search: |
;204/29F |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Edmundson; F. C.
Attorney, Agent or Firm: Hammond & Littell
Claims
We claim:
1. An electrode consisting essentially of an electrically
conductive substrate, an electrocatalytically active material and
an amorphous valve metal oxide binder for adhering said material to
at least a portion of the surface of said substrate, the material
being a particulate solid solution of iridium and ruthenium oxides
having a particle size of less than 0.1 micron, iridium oxide being
present within the range of 1.0-99 mole percent, the balance being
ruthenium oxide.
2. An electrode as in claim 1 wherein the substrate is a metal
selected from the group consisting of titanium and tantalum.
3. An electrode as in claim 1 wherein the binder is an amorphous
oxide selected from the group consisting of tantalum and niobium
oxides.
4. An electrode consisting essentially of an
electrically-conductive substrate, an electrocatalytically-active
material and an amorphous valve metal oxide binder for adhering
said material to at least a portion of the surface of said
substrate, the material consisting essentially of a particulate
solid solution of at least two platinum group metal oxides having a
particle size of less than 0.1 micron with one oxide being present
with the range of 1 to 99 mole percent and the balance being the
second oxide.
5. An electrode as in claim 4 wherein the substrate is a metal
selected from the group consisting of titanium and tantalum.
6. An electrode as in claim 4 wherein the amorphous binder is an
oxide selected from the group consisting of tantalum and niobium
oxides.
7. An electrode as in claim 4 wherein the material is a solid
solution of at least two oxides selected from the group consisting
of ruthenium, rhodium, palladium and iridium.
Description
BACKGROUND OF THE INVENTION
Dimensionally stable electrodes are known to be useful in a variety
of electrolytic applications such as chlor-alkali electrolysis,
electrowinning, cathodic protection, electroplating,
electro-organic synthesis and the like. Generally, these electrodes
consist of an electrically conductive substrate, inert to the
electrolytic environment, bearing on the surface thereof on
electrically conductive electrocatalytically-active coating.
Typical of such electrodes are valve metal (titanium, tantalum)
substrates coated with a platinum group metal or a mixed oxide
coating of valve and platinum metal oxides, although many others
are known.
Generally, however, no one electrode has proven useful in a variety
of electrochemical applications, the inherent and relatively
uncontrollable and unchangeable properties of the coatings
dictating limited uses. For example, while an electrode composed of
a solid solution coating of ruthenium and titanium oxides on a
titanium substrate is an excellent chlor-alkali anode, it fails
rapidly in environments wherein oxygen is evolved, e.g., aqueous
electrowinning.
STATEMENT OF THE INVENTION
Therefore, it is an object of the present invention to provide a
dimensionally stable electrode useful to advantage in a variety of
electrochemical reactions.
It is a further object of the present invention to provide a method
for obtaining such an electrode, which method allows control of the
electrochemical properties of the resulting electrode.
These and further objects of the present invention will become
apparent to those skilled in the art from the specification and
claims which follow.
There has now been found an electrode comprising an
electrically-conductive substrate, an electrocatalytically active
material and a binder for adhering said material to at least a
portion of the surface of said substrate, the material consisting
essentially of a solid solution of at least two platinum group
metal oxides. Such an electrode may be obtained by applying to an
electrically-conductive substrate a dispersion of said solid
solution in a solution of the binder and heating the thus-coated
substrate in the presence of oxygen.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
By the term "electrically conductive substrate," it is intended to
refer to the metallic support for the electrode. It is essential
that this substrate be resistant to the electrolytic environment in
which it will be employed in order that, upon mechanical failure of
the coating, excessive attack will not occur. A variety of
materials are useful depending upon the intended application.
Often, a valve metal such as titanium, tantalum, zirconium or an
alloy thereof is employed. However, it is not essential that the
entire substrate be of this material. Rather, a core of a more
highly conductive metal, such as copper or aluminum, may be
employed if clad or coated with the valve metal. Alternately, a
valve metal may carry a surface coating designed to alter electrode
properties, such as a platinum metal layer. The physical form of
the substrate is independent of the invention and it may be flat or
shaped, continuous or foraminous, as required and desired for the
particular end use envisioned.
By the term "binder," it is intended to refer to any material,
organic or inorganic, capable of adhering the particulate solid
solution to the underlying substrate in a manner relatively
permanent under the conditions obtaining during use. The binder
itself need not be, and most often is not, electrically conductive,
a sufficient amount of the solid solution being dispersed
throughout the binder to provide a path for current from the
underlying substrate to the electrolyte. Thus, a diverse group of
materials is contemplated, such as the fluorocarbons, e.g.,
polyvinylidene fluoride; sodium silicate (subjected to a subsequent
acid treatment); an inorganic glaze of refractory materials such as
titania or silica glasses, and the like. Particularly preferred,
however, in order to facilitate production and for the results
obtained therewith, are the amorphous oxide binders which may be
obtained by thermal decomposition of a solution of the salts
thereof in the presence of oxygen, especially the amorphous valve
metal oxides and particularly tantalum and niobium oxides. These
latter two oxides have been noted to produce remarkably uniform and
adherent coatings without detracting from the activity of the
electrocatalytic material.
By the phrase "solid solution," it is intended to refer to those
mixtures of platinum group metal oxides in which atoms of the
different platinum metals are randomly distributed throughout the
parent metal oxide crystal lattice, thus giving the resultant solid
solution properties different from either platinum metal oxide
alone or a mere physical combination of same. The platinum group
metals contemplated are ruthenium, rhodium, palladium, osmium,
iridium and platinum, preferably ruthenium, palladium, rhodium and
iridium. Particularly preferred are solid solutions of ruthenium
and iridium oxides. Generally, and in order to achieve the desired
beneficial results, at least one percent of the second platinum
metal oxide must be present in the parent platinum metal oxide
crystal lattice. That is to say, for example, at least one mole
percent of ruthenium oxide must be present in an iridium-ruthenium
system. It is by manipulation of the relative amounts of platinum
metal oxides present that it is possible to control the properties
of the electrodes, particularly with respect to the relative
overvoltages at which different elements are discharged when
employing the electrodes as anodes in aqueous solution.
(Overvoltage referring to the potential in excess of that
theoretically required to discharge the element in question at the
electrode surface.) For example, where the electrode is to be
employed as an anode for the electrolysis of aqueous sodium
chloride, a low chlorine overvoltage may be coupled with a high
oxygen overvoltage, especially when the solid solution is of 25%
RuO.sub.2 /75% IrO.sub.2, on a mole basis, thereby reducing the
likelihood of contamination of the chlorine with oxygen and the
attendant current inefficiency. On the other hand, for use as an
electrowinning anode, a low oxygen overvoltage electrode may be
designed. Still further, an anode employing 92-93% RuO.sub.2 /7-8%
IrO.sub.2 in an amorphous tantalum binder and on a titanium
substrate is particularly suited to use in the electrolysis of
dilute aqueous brine to form hypochlorite.
It has been noted that these solid solution materials are
particularly effective when employed in a particle size of 0.1
micron or less, an advantage being noticed both with respect to
current efficiency and operating life of the resultant
electrode.
Generally, the amount of binder present will be that sufficient to
adhere the particulate solid solution to the underlying substrate
in a continuous fashion without being so much as to completely
isolate the individual particles. This is particularly important
where the binder is not itself electrically-conductive under
conditions of use since, otherwise, disruption of electrical
continuity will result. In most instances, this means that from
0.01-1.0 part by weight of binder will be used per part of
particulate solid solution.
The electrodes of this invention depend for their versatility upon
the formation of the particulate solid solution prior to its
application to the electrode. While this preparation may be
accomplished in a number of ways known to the art, it is preferred,
in order to obtain the material in the desired particle size of
less than 0.1 micron, that the solid solution be precipitated from
an acidic solution of platinum metal salts. Thus, the desired
concentrations of the appropriate metals are dissolved in acid
solution, either jointly or separately followed by combination. The
pH of the solution is then slowly raised, generally to a value in
excess of 8, causing precipitation of the material as a hydrated
oxide. This precipitate is now filtered, washed and dried at a
temperature sufficient to remove the water, e.g., 110.degree. C.
The solid solution of platinum metal oxides is then preferably
heat-treated at a temperature within the range of
300.degree.-900.degree. C preferably 450.degree.-800.degree. C,
still more preferably 600.degree.-700.degree. C, to crystallize and
stabilize same.
Next, a dispersion of the aforesaid particulate solid solution is
formed in a solution containing the desired binder. This solution
may consist of an organic polymeric binder dissolved in an
appropriate solvent, such as polyvinylidene fluoride in
1-methyl-2-pyrrolidinone, or an inorganic salt, such as sodium
silicate, in water, in which case a subsequent acid treatment of
the electrode may be required to "insolubilize" the binder.
Preferably, however, the solid solution will be dispersed in a
solution of a valve metal salt, such as TaCl.sub.5 or NbCl.sub.5,
in an appropriate solvent, such as a combination of water, butyl
alcohol and hydrochloric acid. The salt used will be one
decomposable at elevated temperatures, e.g., within the range of
300.degree.-600.degree. C, and in the presence of oxygen to an
amorphous valve metal oxide. Generally, the amount of solvent
required to form the dispersion is that sufficient to dissolve the
binder, suspend the dispersion and still result in a sufficient
viscosity to facilitate application to the underlying substrate.
Such amounts will vary depending upon the materials involved, the
ratio of binder to solid solution and the like. Amounts within the
range sufficient to form a dispersion containing from 5-50 percent
by weight solids are exemplary.
The electrode is formed by applying the dispersion, e.g., by
brushing, spraying or roller coating, to the surface of the
electrically conductive substrate followed by heating the
thus-coated substrate to a temperature within the range of from
300.degree.-600.degree. C in the presence of oxygen.
In order that those skilled in the art may more readily understand
the invention and certain preferred embodiments by which it may be
carried into effect, the following specific examples are
afforded.
EXAMPLE 1
An electrocatalytic material is prepared by dissolving 34.5 grams
IrCl.sub.3.sup.. xH.sub.2 O (52.9% Ir) in 1 liter of water
containing 25 milliliters HCl and 10 ml HNO.sub.3. After boiling
for 5 minutes and cooling, there is added a solution of 23.3 g
RuCl.sub.3.sup.. xH.sub.2 O (40.7% Ru) in 1 liter of water
containing 10 ml HCl. The pH of the resultant solution is adjusted
to within the range of 1.5 to 2.5 with concentrated KOH and heated
almost to boiling. While hot, a 10 percent aqueous KOH solution is
slowly added, with stirring, to precipitate a hydrous oxide. When a
pH of 10 is obtained, the solution is brought to a boil, cooled and
acidified to a pH of 6.5 with dilute aqueous HCl. The precipitate
is then removed by filtration and washed several times with water,
following which it is dried at about 100.degree. C. Finally, the
oxide is ground and heated in air to a temperature of about
660.degree. C for about 16 hours. The resultant material has a
particle size of less than 0.1 micron and contains 50 mole percent
each of iridium and ruthenium oxides. The X-ray diffraction pattern
shows a single rutile phase with peaks intermediate those of the
pure oxides, thus indicating the formation of a solid solution.
This same procedure is also employed to prepare solid solutions of
other platinum metal oxides by simply altering the identity of the
metal salts used. Likewise, the relative proportions of platinum
metal oxides in the electrocatalytic material are varied by
employing differing amounts of the salts in question.
For testing purposes, electrodes are prepared by forming a
dispersion of 1.0 g of electrocatalytic material, 0.5 g of
anhydrous TaCl.sub.5 and 1 ml HCl (35%) in 10 ml butanol. A
dispersion is then applied to a previously degreased and etched
titanium sheet in two coats, with air drying between coats, before
heating in air at a temperature of 500.degree. C for 5 minutes.
This procedure is repeated three times to give the desired
electrode for test purposes.
The electrodes thus prepared are tested as anodes versus a
saturated calomel electrode in (1) a 300 g/l sodium chloride
solution for chloride evolution and (2) a 1 M H.sub.2 SO.sub.4
solution for oxygen evolution, with the half-cell voltage measured
at 70.degree. C and a current density of 3 amperes/square inch. The
results appear in Table I.
TABLE I ______________________________________ Electrocatalytic
Material Anode (mole %) Half-Cell Voltage
______________________________________ RuO.sub.2 IrO.sub.2 Cl.sub.2
O.sub.2 1 100 -- 1.08 1.23 2 75 25 1.14 1.38 3 50 50 1.13 1.36 4 25
75 1.15 1.55 5 -- 100 1.09 1.40
______________________________________
From this table, it can be seen that the relative chlorine and
oxygen overvoltages vary with the composition of the
electrocatalytic material, the material containing 75% IrO.sub.2
showing the greatest displacement and therefore being most
efficient with respect to the loss of current to oxygen generation
in sodium chloride electrolysis.
EXAMPLE 2
For the purpose of comparison, Anode No. 4 of Example 1 is compared
with an anode prepared in the same manner, with the exception that
the electrocatalytic material, rather than being a solid solution
of platinum metal oxides is a mixture, in the same proportions, of
separately prepared IrO.sub.2 and RuO.sub.2. By this procedure, an
oxygen half-cell voltage of 1.35, as compared to 1.55 volts for
Anode No. 4, is obtained, thus dictating considerably greater
oxygen evolution during alkali metal chloride electrolysis.
EXAMPLE 3
A further series of anodes is prepared by the procedure of Example
1 with varying amounts of IrO.sub.2 as indicated in Table II below.
The substrate is an etched titanium mesh and four coatingheating
cycles as described in Example 1 are employed. The anodes are used
in the production of sodium hypochlorite by the electrolysis of a
dilute (30 g/l) sodium chloride solution at a temperature of
25.degree. C, and an anode current density of 1.0 a.s.i., opposite
a titanium cathode. Table II indicates the current efficiencies
obtained.
TABLE II ______________________________________ Electrocatalytic
Material Current Efficiency Anode (mole %) (%)
______________________________________ RuO.sub.2 IrO.sub.2 6 96.5
3.5 73.1 7 92.5 7.5 81.7 8 88.5 11.5 66.8 9 84.5 15.5 65.4
______________________________________
From Table II, it is apparent that control of the solid solution
composition dictates its efficiency in various electrochemical
reactions. Further, in Table III, Anode No. 7 is compared with
anodes of the same composition prepared in the same manner, with
the exception that firing of the electrocatalytic material proceeds
at temperatures above and below that previously employed.
TABLE III ______________________________________ Electrocatalytic
Material Firing Current Material Temperature Efficiency Anode (mole
%) (.degree.C) (%) ______________________________________ RuO.sub.2
IrO.sub.2 10 92.5 7.5 500 74.2 7 92.5 7.5 660 81.7 11 92.5 7.5 825
76.5 ______________________________________
It is apparent that temperature has an effect upon the efficiency
of the resultant anode. Thus, the present invention, which allows
preparation of the electrocatalytic material extra the electrode
and hence a wider range of heat treatment, affords a substantial
advantage.
EXAMPLE 4
A further example of the importance of an ability to control the
temperature at which the electrocatalytic material (as opposed to
the entire electrode) is fired, is provided by Table IV. Here Anode
No. 9 from Table II is compared with anodes prepared in identical
fashion with the exception of the indicated variance in firing
temperature. Electrolysis is conducted employing the electrode as
an anode, opposite a titanium sheet cathode (electrode gap 1.5
inches) in 1 M H.sub.2 SO.sub.4 at 35.degree. C and a current
density of 3 a.s.i. The "lifetime" is determined by noting the time
necessary for the cell voltage to rise from an original level of
about 4.0 volts to a value of 8.0 volts, such a rise indicating
passivation (inactivity) of the anode.
TABLE IV ______________________________________ Electrocatalytic
Material Firing Material Temperature Lifetime Anode (mole %)
(.degree.C) (hrs) ______________________________________ RuO.sub.2
IrO.sub.2 12 84.5 15.5 500 14 9 84.5 15.5 660 134 13 84.5 15.5 825
31 ______________________________________
A remarkable and unexpected advantage is observed at elevated
temperatures, especially temperatures on the order of 660.degree.
C. On the other hand, attempts to directly deposit an
iridium-ruthenium oxide solid solution coating on a titanium
substrate at a temperature in excess of 600.degree. C, lead to the
formation of excessive amounts of nonconducting oxides with the
result that the initial half-cell voltage is prohibitively
high.
EXAMPLE 5
To illustrate the use of an electrode of the present invention in
the area of cathodic protection, Anode No. 3 from Example 1 is
employed opposite a titanium metal cathode in synthetic sea water
(28 g/l NaCl) having a pH of 9.5 at a temperature of
21.degree.-26.degree. C and an anode current density of 3.0 a.s.i.
After 6,000 hours continuous operation, there is no change in the
initially favorable operating voltage. By comparison, an anode
comprising a 2:1 mole ratio solid solution coating of TiO.sub.2 and
RuO.sub.2 on a Ti substrate fails (passivates) after 600 hours.
Comparable results obtain on cold (<6.degree. C) sea water
electrolysis to hypochlorite.
EXAMPLE 6
A solid solution is formed by dissolving 34.5 g IrCl.sub.3.sup..
xH.sub.2 O (52.9% Ir) and 25.0 g RhCl.sub.3.sup.. xH.sub.2 O (39.1%
Rh) in one liter of water containing 25 ml HCl. The pH of the
resulting solution is adjusted to pH 1.5 - 2.5 with concentrated
KOH. The hydrous oxides are coprecipitated by slowly adding a 10
percent aqueous KOH solution while stirring until a pH value of 10
is obtained. The solution is then warmed to 60.degree.-80.degree.
C, while maintaining a pH of 10, cooled and filtered. After several
washings with water, the precipitate is dried at about 100.degree.
C. Finally, the oxide is ground and heated in air at 600.degree. C
for 16 hours. The resultant material contains 50 mole percent each
of iridium and rhodium oxides and its X-ray diffraction pattern
shows a single phase corundum structure with peaks displaced from
that of pure Rh.sub.2 O.sub.3. This catalyst, when bound to a
titanium substrate as in Example 1, results in an anode exhibiting
excellent behavior in neutral and basic brine.
EXAMPLE 7
A solid solution is prepared as in Example 1 using 23.3 g
RuCl.sub.3.sup.. xH.sub.2 O (40.7% Ru) and 27.4 g RhCl.sub.3.sup..
xH.sub.2 O (39.1% Rh). The coprecipitated hydrous oxides are fired
at 660.degree. C for 20 hours. This material, containing 10 mole
percent rhodium and 90 mole percent ruthenium oxides, exhibits an
X-ray diffraction pattern showing a single rutile phase with the
peaks shifted from those of pure RuO.sub.2. An anode prepared from
this material has shown excellent behavior in the electrolysis of
brine and in the electrolysis of acid solutions producing
oxygen.
EXAMPLE 8
Another catalyst material is prepared by dissolving 23.3 g
RuCl.sub.3 and 18.5 g PdCl.sub.2 (anhydrous) in 500 ml water,
precipitating the hydrous oxides as in Example 5 and firing at
550.degree. C for 16 hours. The resulting material contains 10 mole
percent palladium and 90 mole percent ruthenium oxides. X-ray shows
a single rutile phase with peaks shifted from pure RuO.sub.2. An
electrode prepared from this electrocatalyst is useful in acidic,
oxygen-evolving applications.
EXAMPLE 9
By the same procedures, 10% PdO.sub.2 - 90% IrO.sub.2 and 10%
PdO.sub.2 - 90% RhO.sub.2 solid solutions are prepared. The Pd-Ir
electrocatalyst, bound to a tantalum substrate with an amorphous
tantalum oxide binder as in Example 1, shows use as a chlor-alkali
anode, as does the Pd-Rh catalyst in amorphous niobium oxide on a
Nb or Ta substrate.
EXAMPLE 10
To illustrate the use of an electrode of the invention in aqueous
electrowinning, an experiment isi conducted in an electrolytic cell
employing a titanium mesh cathode, a porous polyfluorocarbon spacer
(NAFION, trademark of E. I. du Pont de Nemours and Co., Inc.) and
an anode comprising a titanium mesh substrate bearing a coating of
1 part amorphous tantalum oxide and 2 parts of a 90% RuO.sub.2 -
10% IrO.sub.2 solid solution electrocatalyst. The anolyte is a 200
g/l aqueous slurry of chalcopyrite ore concentrate and ferric
chloride in 10% HCl. Hydrochloric acid (10%) is also the medium for
the catholyte which is a leach of cuprous, ferric and ferrous ions
from the ore slurry. Electrolysis is conducted initially at a
temperature of 30.degree. C and an anode current density of 0.3
a.s.i. (electrode gap, 0.75 inch), the operating cell voltage being
5.15. Copper metal (powder) and H.sub.2 are the cathode products
while Cl.sub.2, CuCl, FeCl.sub.2, S and H.sub.3 O.sup.+ are all
found in the anolyte (the important effect being the dissolution of
additional copper values for later reduction on recycle to the
catholyte). At 1.0 a.s.i., a voltage of 17.7 follows. Changing the
operating temperature to 54.degree. C reduces voltages to 3.45 and
9.35 at 0.3 and 1.0 a.s.i., respectively.
While the invention has been described with reference to certain
preferred embodiments thereof, it is not to be so limited since
changes and alterations may be made therein, while still remaining
within the intended scope of the appended claims.
* * * * *