U.S. patent application number 12/363162 was filed with the patent office on 2010-08-05 for electrochemical methods of making nanostructures.
Invention is credited to Shrisudersan Jayaraman.
Application Number | 20100193363 12/363162 |
Document ID | / |
Family ID | 42396800 |
Filed Date | 2010-08-05 |
United States Patent
Application |
20100193363 |
Kind Code |
A1 |
Jayaraman; Shrisudersan |
August 5, 2010 |
ELECTROCHEMICAL METHODS OF MAKING NANOSTRUCTURES
Abstract
Electrochemical methods for making nanostructures, for example,
titanium oxide (TiO.sub.2) nanostructures are described. The
morphology of the nanostructures can be manipulated by controlling
reaction parameters, for example, solution composition, applied
voltage, and time. The methods can be used at ambient conditions,
for example, room temperature and atmospheric pressure and use
moderate electric potentials. The methods are scalable with a high
degree of controllability and reproducibility.
Inventors: |
Jayaraman; Shrisudersan;
(Painted Post, NY) |
Correspondence
Address: |
CORNING INCORPORATED
SP-TI-3-1
CORNING
NY
14831
US
|
Family ID: |
42396800 |
Appl. No.: |
12/363162 |
Filed: |
January 30, 2009 |
Current U.S.
Class: |
205/74 ;
977/840 |
Current CPC
Class: |
C25D 11/26 20130101 |
Class at
Publication: |
205/74 ;
977/840 |
International
Class: |
C25D 1/00 20060101
C25D001/00 |
Claims
1. A method of making nanostructures, the method comprising:
providing an electrolytic cell, which comprises an anode and a
cathode disposed in an electrolyte comprising a hydroxide, wherein
the anode or the cathode comprise a surface exposed to the
electrolyte; and applying an electrical potential to the
electrolytic cell for a period of time sufficient to obtain
nanostructures on the surface of the anode or the cathode exposed
to the electrolyte.
2. The method according to claim 1, wherein the surface of the
anode or the cathode exposed to the electrolyte comprises a metal
oxide, a mixed metal oxide, a metal, a mixed metal, a metal alloy,
a metal alloy oxide, or combinations thereof.
3. The method according to claim 1, wherein the nanostructures
comprise a metal oxide, a mixed metal oxide, a metal, a mixed
metal, a metal alloy, a metal alloy oxide, a metal hydroxide, or
combinations thereof.
4. The method according to claim 3, wherein the nanostructures
further comprise a borate, a phosphate, a carbonate, a boride, a
phosphide, a carbide, an intercalated alkali metal, an intercalated
alkali earth metal, an intercalated hydrogen, a sulfide, a nitride,
or combinations thereof.
5. The method according to claim 1, wherein the anode and the
cathode each comprise a surface exposed to the electrolyte.
6. The method according to claim 1, wherein the hydroxide is
selected from sodium hydroxide, potassium hydroxide, and
combinations thereof.
7. The method according to claim 6, wherein the electrolyte further
comprises one or more additives.
8. The method according to claim 7, wherein the additives are
selected from boric acid, phosphoric acid, carbonic acid, sodium
sulfate, potassium sulfate, sodium sulfite, potassium sulfite,
sodium sulfide, potassium sulfide, sodium phosphate, potassium
phosphate, sodium nitrate, potassium nitrate, sodium nitrite,
potassium nitrite, sodium carbonate, potassium carbonate, sodium
bicarbonate, potassium bicarbonate, a sodium halide, a potassium
halide, a surfactant, and combinations thereof.
9. The method according to claim 8, wherein the surfactant is
ionic, nonionic, biological, or combinations thereof.
10. The method according to claim 6, wherein the electrolyte is at
a concentration of from 1 molar to 10 molar.
11. The method according to claim 1, wherein the anode and cathode
independently comprise a material selected from a uniform metal, a
metal layer, a metal foil, a metal alloy, multiple metal layers, a
mixed metal layer, multiple mixed metal layers and combinations
thereof.
12. The method according to claim 11, wherein the material is
disposed on a conductive support, a non-conductive support, or
combinations thereof.
13. The method according to claim 12, wherein the conductive
support comprises a material selected from a metal, a metal alloy,
nickel, stainless steel, indium tin oxide (ITO), copper, and
combinations thereof.
14. The method according to claim 12, wherein the non-conductive
support comprises a material selected from a polymer, plastic,
glass, and combinations thereof.
15. The method according to claim 1, wherein the potential is
greater than 0.0 volts.
16. The method according to claim 1, wherein the potential is 5.0
volts or less.
17. The method according to claim 1, wherein the potential is
applied continuously for 1 minute or more.
18. The method according to claim 1, wherein the potential is
applied for 24 hours or less.
19. The method according to claim 1, further comprising cleaning
the anode and cathode prior to contacting the electrolyte.
20. The method according to claim 1, further comprising cleaning
the anode and the cathode after obtaining the nanostructures.
21. The method according to claim 20, wherein cleaning comprises
acid washing.
22. The method according to claim 21, wherein the acid is selected
from hydrochloric, sulfuric, nitric, and combinations thereof.
23. The method according to claim 1, which comprises making the
nanostructures in a batch process.
24. The method according to claim 1, which comprises making the
nanostructures in a continuous process.
25. The method according to claim 1, further comprising heating the
electrolyte to a temperature of from 20 degrees Celsius to 80
degrees Celsius.
26. A method of making titania nanostructures, the method
comprising: providing an electrolytic cell, which comprises an
anode and cathode disposed in an electrolyte, wherein the anode or
the cathode comprise a titanium surface exposed to the electrolyte;
and applying an electrical potential to the electrolytic cell for a
period of time sufficient to obtain titania nanostructures on the
titanium surface of the anode or the cathode exposed to the
electrolyte.
Description
BACKGROUND
[0001] 1. Field of the Invention
[0002] Embodiments of the invention relate to methods of making
nanostructures and more particularly to electrochemical methods of
making nanostructures.
[0003] 2. Technical Background
[0004] Metal oxides, metals, mixed metals, metal alloys, metal
alloy oxides, and metal hydroxides are material systems explored,
in part, due to these systems having several practical and
industrial applications. Metal oxides, for example, titanium (IV)
oxide (titania), are used in a wide range of applications such as
in paints, cosmetics, catalysis, and bio-implants.
[0005] Nanomaterials possess unique properties that are not
observed in the bulk material, for example, the optical,
mechanical, biochemical and catalytic properties of particles are
closely related to the size of the particles. In addition to very
high surface area-to-volume ratios, nanomaterials exhibit
quantum-mechanical effects which can enable applications that are
otherwise impossible using the bulk material. One of the challenges
with nanotechnology is the manufacture of nanomaterials in an
economically viable process. As a result, only a very few
nanotechnology based applications have been commercialized,
although a wide spectrum of nanotechnology based applications have
been demonstrated on a laboratory scale.
[0006] Titania, for example, is a material system where
nanotechnology based applications have been demonstrated on a
laboratory scale and where the nanomaterials could be used in a
wide range of practical applications. Titania nanomaterials can be
used, for example, in photovoltaic applications such as
dye-sensitized solar cells, metal-semiconductor Junction Schottky
Diode solar cells, and doped-TiO.sub.2 nanomaterials based solar
cells. Titania nanomaterials can be used in photocatalysis,
photo-degradation of various organic pollutants, for example,
Rhodamine B, Chloroform, Acid Orange II, Phenol, Salicylic Acid,
and Chlorophenols. Further, titania nanomaterials are useful in
hydrogenation reactions, for example, hydrogenation of propyne
(CH.sub.3CCH), photocatalytic water splitting. Also, titania
nanoparticles can be used in electrochromic devices such as
electrochromic windows and displays, in hydrogen storage, in
sensing applications, for example, humidity sensing and gas sensing
such as in hydrogen, oxygen, carbon monoxide, methanol, and ethanol
sensors. Titania nanomaterials can be used in lithium batteries as
insertion electrodes.
[0007] There are several conventional methods for the synthesis of
nanomaterials such as titania nanostructures, for example, sol-gel,
micelle and inverse micelle, sol, hydrothermal, solvothermal,
direct oxidation, chemical vapor deposition, physical vapor
deposition, electrodeposition, sonochemical, microwave, organic
templated synthesis, aerogel, and TiO.sub.2 nanosheets, for
example, through delaminated layer synthesis from protonic
titanate.
[0008] In conventional sol-gel methods, a colloidal suspension or
sol is formed from precursors, typically inorganic metal salts or
metal-organic compounds, for example, metal alkoxides through
hydrolysis and polymerization reactions. Loss of solvent and
complete polymerization leads to the transition into a sol-gel
phase which is then converted into a dense ceramic through further
drying and heat treatment. Typical synthesis of titanium oxide
nanostructures using the sol-gel method includes adding titanium
alkoxide (e.g. titanium tetraisopropoxide) precursor to a base such
as tetramethyl ammonium hydroxide at 2.degree. C. in alcoholic
solvents. This is followed by heating at from 50.degree. C. to
60.degree. C. for 13 days or at from 90.degree. C. to 100.degree.
C. for 6 hours and finally subjecting to a secondary treatment
involving heating in an autoclave or highpressure reactor at from
175.degree. C. to 200.degree. C.
[0009] Conventional sol-gel methods employ extreme process
conditions, for example very low temperature to high temperatures
and pressures with high energy requirements, requires high pressure
reactors with increased capital costs and uses chemicals, for
example, isopropoxides that involve increased handling costs.
[0010] In conventional hydrothermal methods, hydrothermal synthesis
is performed in an autoclave or high pressure reactor with
Teflon.RTM. liners under controlled temperature and pressure with
the reactions occurring in aqueous solutions.
[0011] A variation of this method is the solvothermal method
wherein organic solvents are used instead of an aqueous
environment. Typical synthesis of titanium oxide nanowires involves
reacting titanium chloride with an acid or inorganic salt at from
50.degree. C. to 150.degree. C. in an autoclave for 12 hours. This
is followed by washing powders of nanomaterial in DI water and
ethanol and drying at 60.degree. C. for several hours.
[0012] Some of the other conventional hydrothermal methods for
making titania nanoparticles are hydrothermal reaction of titanium
butoxide (in isopropanol) with water (water:Ti ratio of 150:1) at
70.degree. C. for 1 hour followed by filtration and heat treatment
at 240.degree. C. for 2 hours and finally washing in DI water
and/or ethanol and drying at 60.degree. C.; hydrothermal reaction
of titanium alkoxide precursor in acidic ethanol-water solution at
240.degree. C. for 4 hrs followed by washing and drying; and a
method of making TiO.sub.2 nanowires through a hydrothermal
treatment of TiO.sub.2 powder in from 10 molar to 15 molar sodium
hydroxide at from 150.degree. C. to 200.degree. C. for from 24
hours to 72 hours followed by washing and drying.
[0013] Conventional hydrothermal methods have disadvantages similar
to the sol-gel method, for example, high cost autoclaves, use of
chemicals that require careful handling, in addition to being
time-consuming and having expensive post-processing treatments.
[0014] In conventional electrodeposition methods, titania nanowires
are deposited using an anodic alumina membrane (AAM) as template.
The synthesis is carried out in a titanium chloride solution (at
pH=2) using pulsed electrodeposition. The substrate is subsequently
heated to 500.degree. C. for 4 hours followed by removal of the AAM
template. A prerequisite for this method is the availability of a
template that can be removed without leaving any residue using a
moderate removal process. Otherwise, regular electrodeposition
yields bulk sized particles. Additionally, handling of corrosive
electrolyte like titanium chloride in an industrial process can be
challenging.
[0015] In conventional direct oxidation methods, synthesis of
titania nanotubes involves applying a voltage of from 10 volts to
20 volts for from 10 minutes to 30 minutes between two titanium
plates in a 0.5% hydrogen fluoride (HF) solution. The use of HF
makes this process unattractive for industrial production. Also,
the shape of the nanostructures obtained is limited to
nanotubes.
[0016] Conventional methods of making titania nanostructures are
energy intensive, employ expensive capital equipment, for example,
high pressure reactors, involve tedious process steps, for example,
cleaning, washing and drying of powders, and use nonbenign
chemicals, for example, alkoxides, titanium chloride, and HF.
[0017] It would be advantageous to have method of making
nanostructures in large quantities in an economically viable
fashion.
SUMMARY
[0018] Methods of making nanostructures, as described herein,
address one or more of the above-mentioned disadvantages of
conventional methods of making nanostructures, for example, titania
nanostructures, and provide one or more of the following
advantages: increased compositional and size control with reduced
capital and/or manufacturing costs and, since the nanostructures
can be grown directly on substrates, the nanostructures possess an
inherently high electrical conductivity. Inherently high electrical
conductivity is particularly useful in photovoltaic and
photocatalytic applications and can lead to materials and systems
with improved architecture.
[0019] One embodiment is a method of making nanostructures. The
method comprises providing an electrolytic cell, which comprises an
anode and a cathode disposed in an electrolyte comprising a
hydroxide, wherein the anode or the cathode comprise a surface
exposed to the electrolyte; and applying an electrical potential to
the electrolytic cell for a period of time sufficient to obtain
nanostructures on the surface of the anode or the cathode exposed
to the electrolyte.
[0020] Another embodiment is a method of making titania
nanostructures. The method comprises providing an electrolytic
cell, which comprises an anode and cathode disposed in an
electrolyte, wherein the anode or the cathode comprise a titanium
surface exposed to the electrolyte; and applying an electrical
potential to the electrolytic cell for a period of time sufficient
to obtain titania nanostructures on the titanium surface of the
anode or the cathode exposed to the electrolyte.
[0021] Additional features and advantages of the invention will be
set forth in the detailed description which follows, and in part
will be readily apparent to those skilled in the art from the
description or recognized by practicing the invention as described
in the written description and claims hereof, as well as the
appended drawings.
[0022] It is to be understood that both the foregoing general
description and the following detailed description are merely
exemplary of the invention, and are intended to provide an overview
or framework for understanding the nature and character of the
invention as it is claimed.
[0023] The accompanying drawings are included to provide a further
understanding of the invention, and are incorporated in and
constitute a part of this specification. The drawings illustrate
one or more embodiment(s) of the invention and together with the
description serve to explain the principles and operation of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The invention can be understood from the following detailed
description either alone or together with the accompanying drawing
figures.
[0025] FIG. 1 is an electrolytic cell used in a method according to
one embodiment.
[0026] FIG. 2a and FIG. 2b show the cyclic voltammetry of a Ti
substrate.
[0027] FIG. 3a, FIG. 3b, FIG. 3c, FIG. 3d are SEM micrographs of
titania nanostructures made according to one embodiment.
[0028] FIG. 4a, FIG. 4b, FIG. 4c, FIG. 4d are SEM micrographs of Ti
electrodes.
[0029] FIG. 5a, FIG. 5b are SEM micrographs of titania
nanostructures made according to one embodiment.
[0030] FIG. 6a, FIG. 6b are SEM micrographs of titania
nanostructures made according to one embodiment.
[0031] FIG. 7a, FIG. 7b are cross-sectional SEM micrographs of the
embodiment shown in FIG. 5a.
[0032] FIG. 8a, FIG. 8b, FIG. 8c, FIG. 8d are a series of SEM
micrographs at increasing magnifications of the embodiment shown in
FIG. 6a.
DETAILED DESCRIPTION
[0033] Reference will now be made in detail to various embodiments
of the invention, examples of which are illustrated in the
accompanying drawings. Wherever possible, the same reference
numbers will be used throughout the drawings to refer to the same
or like parts.
[0034] One embodiment is a method of making nanostructures. The
method comprises providing an electrolytic cell 100, as shown in
FIG. 1, which comprises an anode 10 and a cathode 12 disposed in an
electrolyte 14 comprising a hydroxide, wherein the anode or the
cathode comprise a surface 17 exposed to the electrolyte; and
applying an electrical potential to the electrolytic cell for a
period of time sufficient to obtain nanostructures on the surface
of the anode or the cathode exposed to the electrolyte.
[0035] According to another embodiment, the anode and the cathode
each comprise a surface 16 exposed to the electrolyte as shown in
FIG. 1. In another embodiment, the anode and the cathode each
comprise at least two surfaces exposed to the electrolyte. The
nanostructures can be obtained for instance on the surface of an
anode exposed to the electrolyte, on the surface of a cathode
exposed to the electrolyte, or on the surface of both an anode and
a cathode exposed to the electrolyte.
[0036] Reference to "a surface" or "the surface" of an anode or a
cathode therefore includes one or several surfaces of the anode or
the cathode, or both the anode and the cathode, when either is
exposed to the electrolyte or having nanostructures obtained
thereon.
[0037] According to one embodiment, the surface of the anode or the
cathode exposed to the electrolyte comprises a metal oxide, a mixed
metal oxide, a metal, a mixed metal, a metal alloy, a metal alloy
oxide, or combinations thereof.
[0038] The nanostructures, in one embodiment, comprise a metal
oxide, a mixed metal oxide, a metal, a mixed metal, a metal alloy,
a metal alloy oxide, a metal hydroxide, or combinations thereof.
For example, when the nanostructures comprise a metal oxide, the
metal oxide can comprise, for example, titanium oxide, molybdenum
oxide, zinc oxide, cobalt oxide, or some other metal oxide. For
example, when the nanostructures comprise a mixed metal or a mixed
metal oxide, the nanostructures can comprise a mixture of two or
more metals or metal oxides.
[0039] Several combinations of nanostructures can be obtained after
electrochemical processing such as, when a surface exposed to the
electrolyte comprises a metal, a mixed metal, and/or a metal alloy,
then the metal or metals could be converted to an oxide or
hydroxide or could remain a metal. For instance, all of the metals,
one or more of the metals, or none of the metals could be converted
to an oxide or hydroxide, or any combination thereof. Conversion of
the metal(s) to an oxide or a hydroxide can be dependent upon the
specific starting material, for example, dependent upon the
material's electrochemical behavior when exposed to the
electrolyte.
[0040] Several combinations of nanostructures can be obtained after
electrochemical processing such as, when a surface exposed to the
electrolyte comprises a metal oxide, a mixed metal oxide, or a
metal alloy oxide. Conversion of the metal oxides to a metal or a
hydroxide can be dependent upon the specific starting material, for
example, dependent upon the material's electrochemical behavior
when exposed to the electrolyte. In the case of a metal oxide upon
electrochemical processing according to the methods described
herein, the metal oxides can, in some embodiments, remain oxides
but the stoichiometry may change. For example, in the case of
cobalt oxide, when a surface comprises Co.sub.3O.sub.4, after
electrochemical processing, the composition of the nanostructures
can remain Co.sub.3O.sub.4 or can be converted to CoO or can be
converted to Co or a combination thereof. For example, in the case
of cobalt oxide, when a surface comprises CoO, after
electrochemical processing the composition of the nanostructures
can remain CoO or can be converted to Co.sub.3O.sub.4 or can be
converted to Co or combinations thereof.
[0041] In one embodiment, the electrolyte further comprises one or
more additives. The additives, in one embodiment, are selected from
boric acid, phosphoric acid, carbonic acid, sodium sulfate,
potassium sulfate, sodium sulfite, potassium sulfite, sodium
sulfide, potassium sulfide, sodium phosphate, potassium phosphate,
sodium nitrate, potassium nitrate, sodium nitrite, potassium
nitrite, sodium carbonate, potassium carbonate, sodium bicarbonate,
potassium bicarbonate, a sodium halide, a potassium halide, a
surfactant, and combinations thereof. The surfactant can be ionic,
nonionic, biological, or combinations thereof.
[0042] Exemplary ionic surfactants are (1) anionic (based on
sulfate, sulfonate or carboxylate anions), for example,
perfluorooctanoate (PFOA or PFO), perfluorooctanesulfonate (PFOS),
sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, and other
alkyl sulfate salts, sodium laureth sulfate, also known as sodium
lauryl ether sulfate (SLES), alkyl benzene sulfonate, soaps, and
fatty acid salts; (2) cationic (based on quaternary ammonium
cations), for example, cetyl trimethylammonium bromide (CTAB)
(a.k.a. hexadecyl trimethyl ammonium bromide), and other
alkyltrimethylammonium salts, cetylpyridinium chloride (CPC),
polyethoxylated tallow amine (POEA), benzalkonium chloride (BAC),
and benzethonium chloride (BZT); (3) zwitterionic (amphoteric), for
example, dodecyl betaine, cocamidopropyl betaine, and coco ampho
glycinate.
[0043] Exemplary nonionic surfactants are alkyl poly(ethylene
oxide), alkylphenol poly(ethylene oxide), copolymers of
poly(ethylene oxide) and poly(propylene oxide) (commercially called
Poloxamers or Poloxamines), alkyl polyglucosides (including: octyl
glucoside, decyl maltoside), fatty alcohols (including: cetyl
alcohol, oleyl alcohol), cocamide MEA, cocamide DEA, and
polysorbates (including: Tween 20, Tween 80, dodecyl dimethylamine
oxide).
[0044] Exemplary biological surfactants are micellular-forming
surfactants or surfactants that form micelles in solution, for
example, DNA, vesicles, and combinations thereof.
[0045] By incorporating one or more surfactants in the electrolyte,
the nanostructures can become ordered, for example, similar to
self-assembly.
[0046] According to one embodiment, the nanostructures further
comprise a borate, a phosphate, a carbonate, a boride, a phosphide,
a carbide, an intercalated alkali metal, an intercalated alkali
earth metal, an intercalated hydrogen, a sulfide, a nitride, or
combinations thereof. The composition of the nanostructures can be
dependent on the selection of the additive or additives
incorporated in the electrolyte. For example, titania
nanostructures can be caused to further comprise sodium or
potassium in the nanostructure matrix by adding sodium sulfate or
potassium sulfate in the electrolyte prior to electrochemical
processing, cadmium nanostructures can be caused to further
comprise cadmium sulfide by adding sodium sulfite, sodium sulfide,
sodium sulfate, or combinations thereof in the electrolyte prior to
electrochemical processing.
[0047] The potential can be applied via a power supply 18, for
example, a direct current (DC) power supply which can supply a
constant voltage or a bipotentiostat, for example, which can supply
a cyclic voltage. The potential is not limited to a cyclic voltage,
for example, any potential program can be used according to the
method. A triangular wave, a pulsed wave, a sine wave, a staircase
potential, or a saw-tooth wave are exemplary potential programs.
Other applicable potential programs could be used such as other
potential programs known by those skilled in the art. In one
embodiment, the potential is greater than 0.0 volts. In another
embodiment, the potential is 0.5 volts or more. In another
embodiment, the potential is 5 volts or less, for example, in the
range of from 0.6 volts to 5.0 volts. The potential, according to
one embodiment, is applied continuously for 1 minute or more. The
potential, according to another embodiment is applied for 24 hours
or less. The potential, in some embodiments, is applied
continuously for from 30 minutes to 24 hours, for example, for 4
hours to 18 hours.
[0048] In one embodiment, the electrolyte is a solution comprising
sodium hydroxide, potassium hydroxide, or combinations thereof. The
solution, in some embodiments, can be at a concentration of from 1
molar to 10 molar, for example, at a concentration of from 3 molar
to 8 molar, for example, 5 molar.
[0049] In one embodiment, the anode and cathode independently
comprise a material selected from a uniform metal, a metal layer, a
metal foil, a metal alloy, multiple metal layers, a mixed metal
layer, multiple mixed metal layers and combinations thereof. The
layer(s) can be, in some embodiments, a thick film, a thin film, a
mesh, a patterned layer where the metal(s) is/are present in
strips, discrete areas, a spot, spots, or combinations thereof. An
example of a mixed metal layer is a co-deposited alloy.
[0050] In one embodiment, the pattern comprises the same material.
In another embodiment, the pattern comprises any number of
dissimilar materials, for example, a strip of metal could be next
to a spot of mixed metal, which is next to a square of metal alloy.
The strip, spot, and square could be touching or could be spaced
apart from each other.
[0051] In another embodiment, the same material can be layered on
top of each other. In another embodiment, different materials can
be layered on top of each other, for example, one metal on top of
an alloy, on top of a mixed metal, with several combinations
envisioned.
[0052] The metal film can be, for example, a thin film or a thick
film of Ti metal. The thin film can be, for example, from a few
nanometers in thickness to a few microns in thickness. The thick
film can be, for example, from tens of microns in thickness to
several hundreds of microns in thickness. The electrical
conductivity of the Ti surface can facilitate electron transfer at
the solid-liquid interface and the electrical connection given to
the Ti portion of the substrate. The substrate can comprise a flat
surface or can comprise a non-flat surface. The substrate can be a
flexible substrate or a substrate with a deformable surface.
[0053] According to one embodiment, the material is disposed on a
conductive support, a non-conductive support, or combinations
thereof.
[0054] According to one embodiment, the conductive support
comprises a material selected from a metal, a metal alloy, nickel,
stainless steel, indium tin oxide (ITO), copper, and combinations
thereof.
[0055] The non-conductive support, according to one embodiment,
comprises a material selected from a polymer, plastic, glass, and
combinations thereof.
[0056] For example, in one embodiment, the anode and the cathode
can comprise a material selected from titanium metal, titanium
foil, titanium film disposed on a conductive support, titanium film
disposed on a non-conductive support, and combinations thereof.
[0057] The conductive support, in some embodiments, comprises a
material selected from ITO, copper, and combinations thereof. The
conductive support, in some embodiments, is any conductive metallic
substrate. The non-conductive support, in some embodiments,
comprises a material selected from a polymer, plastic, glass, and
combinations thereof.
[0058] The method can further comprise cleaning the substrates
prior to contacting the electrolyte.
[0059] In one embodiment, the method can be used at ambient
conditions, for example, room temperature and atmospheric pressure
and can utilize low voltage and current, thus, lower energy. In
another embodiment, the method further comprises heating the
electrolyte to a temperature of from 15 degrees Celsius to 80
degrees Celsius, for example, from 30 degrees Celsius to 80 degrees
Celsius, for example, from 30 degrees Celsius to 60 degrees
Celsius. Heating the electrolyte can be realized by a number of
heating methods known in the art, for example, a hot plate placed
under the electrolytic cell. The temperature can be adjusted
depending on desired nanostructures and materials used.
[0060] In one embodiment, the method further comprises agitating
the electrolyte. Any number of agitation methods known in the art
can be used to agitate the electrolyte, for example, a magnetic
stirring bar placed in the electrolyte with a stirrer placed under
the electrolytic cell. Mechanical stirring or ultrasonic agitation,
for example, can also be used.
[0061] According to one embodiment, the method further comprises
cleaning the anode and the cathode after obtaining the
nanostructures. The cleaning, in some embodiments, comprises acid
washing. The acid can be selected from hydrochloric, sulfuric,
nitric, and combinations thereof.
[0062] Another embodiment is a method of making titania
nanostructures. The method comprises providing an electrolytic
cell, which comprises an anode and cathode disposed in an
electrolyte, wherein the anode or the cathode comprise a titanium
surface exposed to the electrolyte; and applying an electrical
potential to the electrolytic cell for a period of time sufficient
to obtain titania nanostructures on the titanium surface of the
anode or the cathode exposed to the electrolyte. In another
embodiment, the anode and cathode each comprise a titanium surface
exposed to the electrolyte.
EXAMPLES
[0063] Annealed, 99.5% titanium substrates available from Alfa
Aesar were cut and cleaned by being sonicated in 1:1:1 mixture of
acetone, iso-propanol, and water for 15 minutes. The titanium
substrates were then rinsed in deionized (DI) water and further
sonicated in DI water for 15 minutes. The titanium substrates were
dried under a stream of nitrogen.
[0064] The electrolyte was prepared using certified ACS sodium
hydroxide and certified ACS potassium hydroxide, both available
from Alfa Aesar, in DI water.
[0065] Electrolytic cells, for example, electrochemical cells of
different sizes (1.5''.times.1''.times.1'' and
3''.times.1.5''.times.3.5'' internal dimensions) were made using
Teflon. Teflon was chosen since Teflon is stable in basic
environment as opposed to glass or metal vessels that can be
susceptible to etching and/or corrosion effects. Other materials
that are resistive to a basic pH can be used to build the
electrochemical cells.
[0066] A bipotentiostat, model AFRDE5, available from PINE
Instrument Company, Grove City, Pa., was used to perform cyclic
voltammetry methods. Constant voltage methods were performed using
a DC power supply, Model E36319, available from Agilent. In the
examples, similarly sized Ti substrates were used as both the anode
and as the cathode.
[0067] FIG. 2a and FIG. 2b show the cyclic voltammetry of a Ti
substrate in 1 molar (M) NaOH and 1M KOH solutions. As shown in
FIG. 2a, during the anodic cycle (positive sweep) there are no
surface reactions up to a potential of about 0.6 volts (V) (as
indicated by zero current). At potentials above 0.6 V, the current
increases indicating the onset of oxidation reactions on the
surface. As the surface potential is increased, a peak is observed
at 1.6 V denoting a diffusion-limited electrochemical reaction.
[0068] It can be hypothesized that the reaction is a surface
oxidation process that may be limited by the mass transfer of the
hydroxyl ions towards the electrode surface. At a potential of 2.3
V, the current increases to further positive values indicating the
onset of further electron-transfer reaction or reactions. From the
trajectory of the current vs. potential curve above 2.3 V, it can
be hypothesized that this second electron-transfer reaction is a
kinetically controlled oxidation reaction that is not affected by
the concentration of hydroxyl ions in the solution (at least at
concentrations>1 M). The cyclic voltammetry can be used as a
guide for predictive experimentation, i.e. the potential to be
applied can be chosen to influence reaction-specific changes to the
surface of the anode and/or the cathode.
[0069] FIG. 2b shows the cyclic voltammetry of a Ti substrate in 1M
KOH. The electrochemical behavior of Ti in KOH and the
electrochemical behavior of Ti in NaOH electrolytes are different,
although the pH of the two solutions is the same. The Ti surface of
the substrate is unaffected at potentials below 0.8 V. At
potentials above 0.8 V, a diffusion-controlled oxidation reaction
up to a potential of 5 V as indicated by a single peak with
positive current. Similar to that from the NaOH system, the cyclic
voltammetry of Ti in the KOH electrolyte can be used a guide for
predictive experimentation to control the surface reactions and
eventually surface structure and/or composition.
[0070] Pre-cleaned titanium substrates (anodes and cathodes) were
placed vertically against the opposing faces of a Teflon cell. The
cell was then filled with electrolyte (NaOH or KOH or a combination
of both). For the examples conducted in the small cell
(1.5''.times.1''.times.1''), 15 mL of electrolyte volume was used
and for the examples in the larger cell
(3''.times.1.5''.times.3.5''), 150 mL of electrolyte was used. The
substrates were then connected to a DC power supply which applied a
preset voltage across the two substrates, now electrodes. The
voltage was chosen based on the cyclic voltammetry results
previously described. Several examples were performed by
systematically changing various experimental conditions. The
results are discussed below.
[0071] Titanium electrodes (anode and cathode) were subjected to
electrochemical control, for example, a constant potential control,
in NaOH and KOH solutions. Solution concentrations of 1 M, 5 M and
10 M were tested and it was found that 5 M solutions produced the
desired titania nanostructures. No or very little nanostructures
were observed on the electrodes that were prepared in 1 M
solutions, even at increased times. In 10 M solutions, although
surface roughness was observed after electrochemical control,
feature sizes were several hundreds of micrometers with little
evidence of nanometer sized structures.
[0072] Based on the above described results, there is an optimal
electrolyte composition range at which TiO.sub.2 nanostructures can
be formed electrochemically. Henceforth herein, the examples
pertain to 5 M solutions of NaOH or KOH or combinations
thereof.
[0073] Controls corresponding to each electrochemical example were
prepared by immersing Ti substrates in the respective electrolyte
for the respective time without any applied potential. Electrodes
were also subjected to varying time (i.e. the time under
electrochemical control). For the electrodes with electrochemical
control for 30 minutes and 2 hours, no nanostructures were observed
both in NaOH and KOH solutions. Scanning electron microscope (SEM)
micrographs of these electrodes (not shown) were similar to those
of the controls.
[0074] FIG. 3a, FIG. 3b, FIG. 3c, and FIG. 3d are SEM micrographs
of Ti substrates that were subjected to a constant potential of 5 V
for 6 hours in 5 M NaOH solution. FIG. 3a and FIG. 3c correspond to
those of the anode (i.e. the surface experiences a positive
potential) and FIG. 3b and FIG. 3d correspond to those of the
cathode (i.e. the surface experiences a negative potential).
[0075] FIG. 3a and FIG. 3b are SEM micrographs of the Ti substrates
after being rinsed in DI water and dried under a nitrogen flow
following electrochemical processing. The titania nanostructures
comprise an open (porous) network 18 connected by short, nanometer
sized (width) TiO.sub.2 nanowires 20. The "grainy" features are
due, in part, to the presence of the leftover NaOH that did not
wash out during DI water rinse. This was confirmed by the presence
of sodium peaks in X-ray diffraction (XRD) analysis.
[0076] FIG. 3c and FIG. 3d are SEM micrographs of the substrates
after being rinsed, acid-washed and dried following electrochemical
processing. For the acid-wash step, the substrates were immersed in
a mild acid, for example, 1 M HCl, for 30 minutes followed by
rinsing in DI water. Well defined titania nanostructures similar to
those observed in FIG. 3a and FIG. 3b are present sans the
graininess. This is due, in part, to the complete removal of NaOH
by acid-washing. The titania nanostructures comprise an open
(porous) network 18 connected by short, nanometer sized (width)
TiO.sub.2 nanowires 20. This represents a very high surface area
surface with very good electrolyte access to the entire surface
through open pores.
[0077] The sizes of the nanowires in these networks ranged between
from 10 nm to 40 nm with an average around 30 nm. These
high-surface area structures possess an increased accessibility for
liquids or gases to the entire surface area or gases which is an
advantageous attribute in applications where material utilization
is to be maximized (e.g. photovoltaic cells).
[0078] Although the exact mechanism of the creation of these
nanostructures is unclear currently, a dissolution-redeposition
mechanism can be hypothesized, wherein the electrolyte accesses a
maximum nm.sup.2 of the surface during the synthesis process. Since
the nanostructures are grown into the metal substrate, the
nanostructures possess increased electron accessibility and
electrical conductivity.
[0079] FIG. 4a, FIG. 4b, FIG. 4c, and FIG. 4d are SEM micrographs
of Ti electrodes that were subjected to a constant potential of 5 V
for 6 hours in 5 M KOH solution. FIG. 4a and FIG. 4c correspond to
those of the anode and FIG. 4b and FIG. 4d correspond to those of
the cathode.
[0080] FIG. 4a and FIG. 4b are SEM micrographs of the Ti substrates
after being rinsed in DI water and dried under a nitrogen flow
following electrochemical processing.
[0081] FIG. 4c and FIG. 4d are SEM micrographs of the substrates
after being rinsed, acid-washed and dried following electrochemical
processing. For the acid-wash step, the substrates were immersed in
a mild acid, for example, 1 M HCl, for 30 minutes followed by
rinsing in DI water. No to minimal discernible nanostructures were
formed under these conditions. FIG. 4a appears to have some
structure on the surface, of which disappears after acid wash, as
shown in FIG. 4c.
[0082] FIG. 5a and FIG. 5b are SEM micrographs of Ti substrates
processed under a constant potential control of 5 V for 16 hours in
5 M NaOH solution. FIG. 5a corresponds to the anode and FIG. 5b
corresponds to the cathode.
[0083] As shown in FIG. 5a, the surface exhibits webbed titania
nanostructures with the connecting titania nanowires 22 having
finer sizes as compared to the 6 hour electrode, shown in FIG. 3a.
The average sizes of the titania nanowires are less than 10 nm and
several titania nanowires are bundled together forming a high
surface area network. On the other hand, the titania nanostructures
24 on the counter electrode seem to have collapsed, since they are
more closed than the corresponding 6 hour electrode, shown in FIG.
3b, possibly due to some sort of a coalescence effect.
Nevertheless, these disordered structures are still in the sub-100
nm regime.
[0084] FIG. 6a and FIG. 6b are SEM micrographs of Ti substrates
processed under a constant potential control of 5 V for 16 hours in
5 M KOH solution. FIG. 6a corresponds to the anode and FIG. 6b
corresponds to the cathode.
[0085] As compared to the 6 hour electrodes shown in FIG. 4a and
FIG. 4b which did not exhibit titania nanostructures, both the
anode and the cathode possess an interwoven network of titania
nanostructures 26, for example, titania nanowires. The titania
nanowires have high surface area and good accessibility to the
titania nanostructures even deep into the substrate. The anode
possesses uniform distribution of sub-10 nm sized titania nanowires
while the cathode possesses titania nanowires that are
predominantly around 30 nm. An advantageous feature of the titania
nanostructures is the amount of surface connectivity. The titania
nanowires are intricately and inseparably connected to each other
to the point where it is almost impossible to identify the start
and end of any given strand of titania nanowire.
[0086] Also, it is clear that the surface structure of the titania
nanostructures can be manipulated by manipulating processing
conditions such as electrolyte composition, time, electrode
polarity (anode vs. cathode), electrode potential or combinations
thereof.
[0087] FIG. 7a and FIG. 7b are cross-sectional SEM micrographs of
the 16 hour electrode synthesized in 5 M NaOH (anode) shown in FIG.
5a. The titanium to titania interface 28 illustrates a good
substrate-to-nanostructure connectivity. The layer of titania
nanostructures 30 across the titanium substrate 32 is fairly
uniform. The average thickness of the layer of nanostructures is
around 500 nm.
[0088] The thickness can be controlled, for example, by controlling
the time of electrochemical control within the optimum time range,
as too little (<6 hours) or too high a time will not yield the
desired nanostructures. For example, a 72 hour experiment (Ti under
potential control in KOH or NaOH) caused the collapse of
nanostructures; this might be due to the mechanical collapse of the
nanostructures as Ti surface is continually being subjected to
continuous dissolution-redeposition.
[0089] Table 1 shows the summary of XRD analysis performed on the
Ti electrodes synthesized in 5 M NaOH and 5 M KOH solutions for 16
hours under electrochemical control. The electrodes were subjected
to heat-treatment prior to XRD analysis. The heat treatment
comprised heating the electrodes to 500.degree. C. at a rate of
10.degree. C. per minute and holding at 500.degree. C. for 1
hour.
TABLE-US-00001 TABLE 1 Phases detected Electrolyte Electrode from
XRD analysis NaOH Control (no electrochemistry) Ti metal Anode Ti
metal TiO.sub.2 - Rutile TiO.sub.2 - Anatase Cathode Ti metal
TiO.sub.2 - Rutile KOH Control (no electrochemistry) Ti metal Anode
Ti metal TiO.sub.2 - Rutile TiO.sub.2 - Anatase Cathode Ti metal
TiO.sub.2 - Rutile
[0090] The controls in both the electrolytes did not yield any
oxides showing that the surface remained in the metallic state. The
anode (working electrode) in both cases showed the presence of
metallic Ti and Rutile and Anatase phases of TiO.sub.2. The
metallic phase is the background from the Ti substrate. The cathode
(counter electrode) exhibited the presence of only the Rutile phase
of TiO.sub.2 in addition to the Ti metal background from the
substrate.
[0091] This feature could be favorably exploited to selectively
synthesize TiO.sub.2 nanostructures with a desired phase or phases.
The nanostructures remained intact after heat treatment. Also, one
could subject these electrodes to further heat treatment to obtain
the desired phases.
[0092] FIG. 8a, FIG. 8b, FIG. 8c, and FIG. 8d are a series of SEM
micrographs of the 16 hour anode synthesized in KOH solution taken
at increasing magnifications (500.times., 2500.times.,
10,000.times. and 25,000.times.) shown in FIG. 6a. This electrode
was chosen for illustrative purposes only; other electrodes show
similar behavior. Moving from FIG. 8a through 8d, the titania
nanostructures are formed uniformly across the entire surface and
not merely discrete islands of nanostructures.
[0093] This is an advantage of using an electrochemical process
where the entire surface can be manipulated uniformly. This has an
important implication in terms of scalability and manufacturability
of this process. A bigger substrate along with a bigger
electrochemical cell can be used to manufacture various quantities
(few mm.sup.2 to several m.sup.2) of TiO.sub.2 nanostructures.
[0094] In one embodiment, the method comprises making the
nanostructures in a batch process. In another embodiment, the
method comprises making the nanostructures in a continuous
process.
[0095] For example, the process could be a batch process where
sheets of Ti or Titanium coated substrates (for example, a Ti film
on an indium tin oxide (ITO) or a copper substrate or a Ti film on
a polymer substrate such as polyethylene terephthalate (PET)) can
be immersed in the electrolyte (NaOH or KOH) and nanostructures
created by applying an electric potential.
[0096] Another embodiment that could be envisioned is a continuous
process wherein two Ti or Ti coated substrate rolls could be
continuously fed into a tank containing NaOH or KOH while electric
potential is being applied. A downstream cleaning and/or rinsing
step could be integrated producing rolls of TiO.sub.2
nanostructured surfaces. Also, since the reaction is limited to the
surface that is in contact with the electrolyte, excellent process
control can be achieved. In both embodiments, the process can be
monitored by monitoring the current as a function of time.
[0097] It will be apparent to those skilled in the art that various
modifications and variations can be made to the present invention
without departing from the spirit or scope of the invention. Thus,
it is intended that the present invention cover the modifications
and variations of this invention provided they come within the
scope of the appended claims and their equivalents.
* * * * *