Journal of The Electrochemical Society, 157 6 B831-B836 2010 B831

0013-4651/2010/1576/B831/6/$28.00 The Electrochemical Society

Electrophoretically Fabricated Diamond Nanoparticle-Based

Electrodes
Lyda La-Torre-Riveros, Keyla Soto, M. Aulice Scibioh, and Carlos R. Cabrera*,z
Center for Advanced Nanoscale Materials, Department of Chemistry, University of Puerto Rico, San
Juan 00936-8377, Puerto Rico

Dimensionally stable, high surface area support for a possible direct methanol fuel cell application was fabricated from commer-
cial diamond nanoparticles through electrophoretic deposition onto silicon wafer substrates, and their electrochemical character-
istics were examined by employing inorganic redox probes such as FeCN63/4 and RuNH363+/2+. As-received diamond
nanoparticles were purified by refluxing in an aqueous nitric acid solution, and the product was characterized by using X-ray
diffraction, X-ray photoelectron spectroscopy, prompt gamma-ray neutron activation analysis, Raman spectroscopy, electron
energy loss spectroscopy, and transmission electron microscopy techniques. Electrophoretically deposited diamond nanoparticle
layers of uniform thickness were obtained by controlling experimental parameters, such as applied voltage, deposition time, and
the concentration of diamond nanoparticles in the suspension. Platinum nanoparticles were electrodeposited onto these diamond
nanoparticle layers Pt/DNP by step and sweep potential method. Their structural and morphological characterizations were made
by using scanning electron microscopy and energy-dispersive X-ray analysis. The electrochemical activity of Pt/DNP toward
methanol oxidation was studied. The present study paves a way to fabricate ultrathin, uniform, high surface area, and dimension-
ally stable diamond electrodes in a controllable fashion. This type of deposited diamond nanoparticle layers may be considered as
catalyst support material for fuel cell applications.
2010 The Electrochemical Society. DOI: 10.1149/1.3374403 All rights reserved.

Manuscript submitted March 25, 2009; revised manuscript received March 2, 2010. Published April 22, 2010.

Fuel cells attract tremendous attention in the present days as
environmentally sustainable systems.1 Especially, direct methanol
fuel cells are developed for transportation and portable power sup-
ply applications. In spite of the numerous demonstration systems,
the commercialization is hampered due to the prohibitively high
costs and durability of materials. Regarding cost reduction, the
noble-metal loadings must drop to a level of 1.0 mg cm2 from
the present 2.08.0 mg cm2, depending on the applications. Load-
ing reduction through increasing platinum utilization is one of the
approaches. Non-noble catalyst development is another approach.
Designing high performance electrodes would be yet another ap-
proach. Dispersing catalysts on electrically conducting, high surface
area carbon materials is a significant step forward to achieve a finer
dispersion of the metal catalyst and to get a high electrochemically
active surface area.2
Carbon is one of the best-known high surface area substrates for
electrocatalysts.3 Different carbons e.g., Vulcan XC72R with
232 m2 /g in surface area and electrical conductivity of
0.1102 S/cm have been tested to find their suitability as catalyst
supports for fuel cell applications.4-6 However, a major problem
with the carbon supports is that they lack chemical stability when
subjected to high positive potentials due to severe oxidation.7,8 Dia-
mond, because of its high density, together with a strong sp3 bond-
ing, is inert to oxidative attack. Nondoped diamond is an electrical
insulator with a wide bandgap 5.4 eV, has low reactivity, and is
chemically and electrochemically inert.9-11 However, as other large
bandgap materials diamond can be made conducting by doping it
with certain elements. Presently, in most cases boron is used as a
dopant, which results in a p-type semiconductor. Another form in
which diamond can be used is as a nanoparticle. Diamond nanopar-
ticles can present different electrochemical characteristics due to its
higher surface to volume ratio e.g., 220 m2 /g from Alit Co.,
Ukraine and particular features carbonoxygen functionalities and
hydrogen terminations on its surface, edges, and facets.12,13 Syn-
thetic nanodiamond powders have been used as a catalyst support
for the oxidation of carbon monoxide to carbon dioxide. These par-
ticles were modified at their surface through thermal and electro-
chemical treatments and by the deposition of metallic palladium on
their surface.14 Conducting diamond thin film, with a surface con-
ductivity of 104105 1 at room temperature, is relatively a new
* Electrochemical Society Active Member.
z
E-mail: carlos.cabrera2@upr.edu
electrode material that has received great attention recently because
it possesses several technologically important characteristics, such
as high corrosion resistance, mechanical stability, and large working
potential window in the order of 3.0 V. Masuda et al.15 succeeded in
fabricating well-ordered nanoporous honeycomb diamond films by
oxygen plasma etching through an alumina mask. Honda et al.16
reported the use of conductive nanoporous honeycomb diamond as a
support for platinum nanoparticles for electrocatalytic applications.
Hian et al.17,18 investigated the properties of nondoped nanocrystal-
line diamond film and found that compared to the boron-doped dia-
mond, it is a highly active electrode material, with low overpoten-
tials and high adherence of metallic electrodeposits, for the redox
systems they have studied. In the present work, dimensionally
stable, high surface area support was fabricated on silicon wafer
substrates from commercial diamond nanoparticles through the elec-
trophoretic deposition EPD technique. We have adopted the EPD
route because it is a very simple and efficient technique to obtain the
desired structure. Diamond nanoparticle layers of uniform thickness
were obtained by controlling experimental parameters, such as ap-
plied voltage, deposition time, and the concentration of diamond
nanoparticles in the suspension. Commercial, as-received, diamond
nanoparticles were purified by refluxing in aqueous nitric acid. The
product of the purification process was characterized by X-ray dif-
fraction XRD analysis, X-ray photoelectron spectroscopy XPS,
Raman spectroscopy, electron energy loss spectroscopy EELS,
prompt gamma-ray neutron activation analysis PGNAA, and trans-
mission electron microscopy TEM techniques. The electrophoreti-
cally deposited diamond nanoparticle layers were characterized by
scanning electron microscopy SEM. The platinum electrodeposi-
tion onto electrophoretically fabricated diamond nanoparticle layer
was performed using the step and sweep potential method developed
in our laboratory,19 and their activity toward methanol oxidation was
studied. Platinum was chosen because carbon supported platinum
nanoparticles have proven to be effective catalysts for fuel cell re-
actions.
Experimental
Chemical pretreatment of diamond nanoparticles. Diamond
nanoparticles 210 nm purchased from Alit Co. Kiev, Ukraine
were subjected to chemical pretreatment to purify and to function-
alize them. The pretreatment was carried out in a reflux system, in
which 2 g of sample was dispersed in concentrated HNO3 and boiled
for 42 h at 130C. Successively, they were filtered and washed with
an excess of nanopure distilled water to neutral pH.20
B832 Journal of The Electrochemical Society, 157 6 B831-B836 2010
Electrophoretic fabrication of diamond nanoparticle layers.
The diamond nanoparticle layers were fabricated by using the EPD
technique as described in an earlier paper.21 In this method, a con-
stant voltage was applied between two pieces of highly conducting
p-Si100 wafers 103 cm, Virginia Semiconductor, Inc.. The mM FeCN63/4 in 1 M KCl solution. Potential was applied to
silicon wafers used were cleaned with concentrated HF for 1 min to
eliminate the surface impurities. The anode and cathode were sepa-
rated at a fixed distance 5 mm, both submerged in a suspension of
chemically pretreated purified diamond nanoparticles dispersed in
isopropanol. Diamond powder did not disperse in water, ethanol, or
isopropanol under normal experimental conditions. However, a soni-
cating process helped to obtain stable electrophoretically active dis-
persions with reproducible properties.22,23 The applied voltage, time
of deposition, and concentration of suspension were tuned to obtain
layers of varying thickness. The thickness of the electrophoretically
deposited diamond nanoparticle layers was determined by using a
scanning electron microscope JEOL 5800 LV.
Electrodeposition of platinum clusters onto diamond layers.
The platinum electrodeposition onto the electrophoretically fabri-
cated diamond layers was achieved by the step and sweep potential
method19 by using aqueous solution of K2PtCl66H2O 5 mM under
nitrogen flux. An Autolab PGSTAT30 computer controlled poten-
tiostat was used. In this method, the voltage was applied as a step at
0.2 V, and then the voltage was swept from 0.6 to the initial
voltage 0.2 V with a scan rate of 30 mV/s. The electrodeposi-
tions were carried out by sweeping the potentials ranging from 10 to
30 cycles by increments of 5. After achieving the platinum elec-
trodeposition, methanol oxidation was carried out in a mixture of 1.0
M methanol in 0.5 M H2SO4 aqueous electrolyte solution under
inert nitrogen atmosphere at room temperature.
Half-cell experiments. The electrochemical measurements
were carried out in a typical three-electrode assembly consisting of
electrophoretically deposited diamond nanoparticles on highly con-
ducting p-Si100 wafers as working electrodes with and without
platinum electrodeposition, Ag/AgCl as a reference electrode, and a
graphite rod as a counter electrode. Currentpotential curves were
recorded by using an Autolab PGSTAT30 computer controlled po-
tentiostat. The working electrode was pressed against the bottom of
the Teflon cell. At first, the potential window of the diamond elec-
trode was determined by using aqueous 0.5 M H2SO4 solution as an
electrolyte. At the start of the experiments, the potential was scanned
between 0.0 and 0.3 V, which was increased until hydrogen evolu-
tion was observed.
The electrochemical response of the electrophoretically depos-
ited diamond nanoparticle layers was tested by employing
FeCN63/4 and RuNH363+/2+ inorganic redox probes dis- ticles were made before and after the purification by using PGNAA.
Figure 1. TEM images of diamond nano-
particles a before and b after chemical
pretreatment.
solved in 1 M KCl. To observe typical electrochemical responses of
these redox couples, after the determination of the potential window,
the cell was cleaned several times with nanopure water
18 M cm. At first, the cell was refilled with an aqueous 1.0
this redox couple from 0.1 to 0.5 V and studied the behavior of
this redox couple at different scan rates: from 10 to 50 mV/s in
increments of 5 mV/s. The same procedure was performed using an
aqueous 1.0 mM RuNH363+/2+ in 1 M KCl solution not shown.
The potential was scanned from 0.0 to 0.5 V. All electrochemical
experiments were repeated several times to confirm the reproducibil-
ity of the process. Different redox systems would differ in their peak
to peak potential difference Ep in the cyclic voltammograms. A
faster electrochemical reaction would exhibit a smaller Ep value.24
Physicochemical characterization. The diamond nanoparticles
purified by chemical pretreatment were subjected to structural and
morphological characterizations by using a Raman spectroscope
Renishaw In Via with a 785 nm line of Ar+ laser, X-ray diffracto-
meter analysis SIEMENS D5000, with Cu K radiation line,
X-ray photoelectron spectroscope PHI5600, Mg K monochro-
matic X-ray source 350 W, transmission electron microscope Ziess
200 kV, and PGNAA University of Missouri at Columbia.20,25
The experimental conditions employed for the PGNAA are neutron
flux, 6 1013 n/cm2 s; exposure time, 11.5 h; and element used,
U-235 high enriched uranium: 20.
The electrophoretically deposited diamond nanoparticle layers
were examined by using a scanning electron microscope JEOL-
5800LV. The platinum clusters electrodeposited onto the diamond
electrodes were characterized by using SEM, energy-dispersive
X-ray EDX spectroscope JEOL-5800LV, and XPS techniques.
Results and Discussion
As-received commercial diamond nanoparticles, which would
have been subjected to stringent purification steps by the manufac-
turer, still contain a low level of impurities. Hence, the commercial
diamond nanoparticles were subjected to chemical pretreatment in
acid reflux by using concentrated HNO3 to remove impurities and to
introduce hydrogen onto the diamond surface. As expected, the pu-
rification process produced significant differences in the commercial
sample, as can be seen in the transmission electron microscope im-
ages. Figure 1a shows layers of amorphous carbon in the cluster
surface of the diamond nanoparticles. This layer is significantly re-
moved after acid treatment, as we could see in Fig. 1b, where the
particles are more dispersed and free of amorphous carbon. In addi-
tion, the hydrogen content measurements for the diamond nanopar-
 Journal of The Electrochemical Society, 157 6 B831-B836 2010
Figure 2. Color online Raman spectra of diamond nanoparticles a before
and b after chemical pretreatment.
The hydrogen content in the as-received diamond nanoparticle
sample and that in the purified samples are 16,300 and 32,400 ppm,
respectively. This increase in the hydrogen content of the purified
sample can be attributed to the effect of the acid treatment, which
might cause the hydrogen atoms to get adsorbed on the diamond
surface. It has been reported that hydrogen termination of the dia-
mond surface gives stability to the diamond.26-30 The surface con-
ductivity of diamond due to hydrogen was reported a decade ago by
Landstrass and Ravi31 and Speranza and Laidani.32 In earlier stud-
ies, undoped diamond films of perfect crystallinity were used, and
the conductivity of those films was assigned to unknown structural
defects caused by the temperature during film deposition.33,34 Gi et
al.35 observed a decrease in the resistance of diamond while it was
in contact with acid or in water vapor and ascribed this drop in
resistance to the formation of a conducting surface film covered with
hydrogen atoms. This p-type conductivity is characterized by a high
carrier density.26,28,36,37 Nevertheless, the role of oxygen in diamond
conductivity was studied by Chakrapani,38 suggesting that a charge
transfer between a water layer containing a redox couple of oxygen
and diamond surface, as well as pH conditions, is responsible for
diamond conductivity.
The Raman spectra of the unpurified and purified diamond nano-
particle samples are shown in Fig. 2. The characteristic peak around
1328 cm1 of the D-band corresponds to the sp3 bonded carbon
atoms. The intensity of this D-band is significantly enhanced in the
purified sample compared to the unpurified sample, showing the
effect of the acid treatment. The results are similar to the Raman
spectra results of the diamond nanoparticles reported.39 There is a
slight improvement in the intensity of the D-band sp3 carbon in the
purified sample compared to the unpurified sample, showing the
effectiveness of the acid pretreatment process.
The predominant presence of sp3 carbon in the diamond nano-
particle samples used in this study is further verified with the EELS
analysis Fig. 3. As shown in Fig. 3a, the EELS of the unpurified
diamond nanoparticle sample exhibited a shoulder around 285 eV
due to the state and a peak at 300 eV due to the states. The
intensity of the peak is extremely lower than that of the peak.
B833
Figure 4. Color online XRD patterns of a unpurified and b purified
diamond nanoparticles by HNO3 reflux process.
Figure 3b shows the EELS of the purified sample, in which the
shoulder peak present in the unpurified sample corresponding to
completely disappears, but the predominant presence of the peak
can be noted. Further, in Fig. 3b, additional peaks present at 312 and
335 eV correspond to the state and attributed to tetrahedral sp3
bonded carbon.40 Figure 4a and b shows typical XRD patterns of
diamond such as 111 at 44 and 220 at 75 corresponding to the
unpurified and purified diamond nanoparticle samples, indicating
that a larger number of 111 and 220 diamond facets are exposed
compared with the unpurified ones.41 Further, the absence of peaks
between 2 20 and 30 shows the absence of an amorphous car-
bon material in the samples.
The EPD technique is convenient to synthesize a desired layer
thickness of solid layers by varying experimental parameters, such
as applied voltage, concentration of nanoparticle in the suspension,
and time of deposition. A more exhaustive analysis of the procedure
was carried out to verify the reproducibility of the experimental
conditions such as temperature and the sonication time to obtain the
suspension. Scanning electron micrographs of electrophoretically
deposited layers of diamond nanoparticles fabricated under the op-
timized experimental conditions of 260 V applied voltage and 40 s
duration of deposition at different suspension concentrations such as
0.1, 0.3, and 0.5% are shown in Fig. 5a-c. For all electrochemical
experiments, we used the electrode with the smallest thickness, just
necessary to cover the silicon substrate and to ensure that only the
diamond particles are in contact with the electrolyte or the redox
system under study.
The cyclic voltammograms of silicon wafer substrates with
dashed line and without diamond thin films solid line while em-
Figure 3. Color online Electron energy
loss spectra of diamond nanoparticles a
before and b after chemical pretreat-
ment.
B834 Journal of The Electrochemical Society, 157 6 B831-B836 2010

Figure 5. SEM images of electrophoreti-

cally deposited layers of diamond nano-
particles onto silicon wafers for a period
of 40 s, at an applied voltage of 260 V,
with different suspension concentrations
such as a 0.1, b 0.3, and c 0.5%.

ploying them as working electrodes in 0.5 M H2SO4 solution are
shown in Fig. 6. The current corresponding to the electrophoretically
deposited diamond nanoparticle layer potential window is limited by
hydrogen evolution at negative potentials and by oxygen evolution
at positive potentials.
The electrochemical response of the electrophoretically depos-
ited diamond layer toward the FeCN63/4 redox couple is
shown in Fig. 7. The peak potential difference Ep values ranged
between 100 mV at a scan rate of 10 mV/s and 128 mV at 50
mV/s. In the electrochemical response of the hexamine ruthe-
niumIII chloride redox couple figure not shown, the Ep values
were closer to those found with FeCN63/4, 101 mV at 10 mV/s
and 131 mV at 50 mV/s. These results show that the electrochemical
process is quasi-reversible. According to the Nernst equation, the
E should be near 59 mV/n for one electron-transfer reaction. Here,
the electron-transfer kinetics is not rapid as the E values were not
constant with the variation in scan rates. The linear relationship was
found between ic cathodic current and 1/2 root square of scan
rate, inset of Fig. 6 indicating the diffusion-controlled process in
the nanodiamond electrode. At slow scan rates, the diffusion layer
would grow much more from the electrode in comparison to a faster
scan rate.11,42
The working electrode was fabricated by electrodepositing plati-
num onto an electrophoretically deposited diamond nanoparticle
layer by the step and sweep potential method, as indicated in the
Experimental section. There are papers on the galvanostatic deposi-
tion of platinum from K2PtCl66H2O in HClO4 solution to obtain
control sized clusters with homogeneous distribution43 and galvano-
static deposition as a function of pulse number and current density
on electrically conducting micro- and nanocrystalline diamond thin
films.44 Methanol oxidation studies were carried out by using plati-
num deposited diamond thin-film electrodes in a half-cell mode.
Figure 8 shows the cyclic voltammetric curves for the methanol
oxidation in 1.0 M CH3OH + 0.5 M H2SO4 aqueous solution at
the sweep rate of 20 mV s1. For clarity, only the electrochemical
responses of the a electrophoretically deposited diamond nanopar-
ticle electrodes and those with b 25 and c 30 cycles of platinum
electrodeposition onto the electrophoretically deposited diamond
nanoparticle layers are shown. The higher current signals of the
methanol oxidation peak are around 18 and 37 A, which corre-
spond to the electrode in which 25 and 30 platinum deposition
cycles were performed, respectively. The cyclic voltammograms
corresponding to 20, 15, and 10 cycles have similar shapes, and the
corresponding current values are 20, 13.5, and 13.0 mA, respec-
tively. These results show that methanol oxidation can be performed
using nondoped diamond nanoparticles as catalytic support.
Figure 9 shows the EDX spectra of the electrode in which 25
platinum deposition cycles were performed and its corresponding
SEM image. The EDX spectra shows the presence of carbon K
line, oxygen K line, silicon K line, and platinum K and L lines.
The corresponding SEM image shows that the electrochemically
deposited platinum particle sizes are less than 1 m. The particle
size is similar or lesser in the other electrodes made with lesser
number of deposition cycles.
Figure 10 shows the XPS spectra of the electrode in which 30
platinum deposition cycles were employed to fabricate the electrode.
Typical platinum 4f5/2 and 4f7/2 lines are present around 7172 eV,
indicating that metallic platinum is deposited on the diamond nano-
particle surface.33,45-48

Figure 6. Cyclic voltammogram of silicon wafer solid line and electro-

phoretically deposited diamond nanoparticles on silicon wafer as working Figure 7. Cyclic voltammogram of FeCN63/4 1.0 mM in KCl 0.1 M, at
electrodes dotted line. H2SO4 0.1 M as supporting electrolyte. Voltage different scan rates, using an electrophoretically deposited diamond nanopar-
range of 0.6 to 0.9 V vs Ag/AgCl at a scan rate of 20 mV/s. ticles on silicon wafer as working electrode.
 Journal of The Electrochemical Society, 157 6 B831-B836 2010
Figure 8. Cyclic voltammograms of methanol 1.0 M in H2SO4 0.5 M at 20
mV/s using as working electrode: a Electrophoretically deposited diamond
nanoparticle layer, b electrophoretically deposited diamond nanoparticle
layer with electrochemically deposited platinum clusters after 25 cycles of
deposition, and c electrophoretically deposited diamond nanoparticle layer
with electrochemically deposited platinum clusters after 30 cycles of depo-
sition. Scan rate is 20 mV/s.
Conclusions
The EPD method has been successfully employed to fabricate
diamond nanoparticle-based electrodes on silicon wafer substrates.
Layers of different thicknesses can be obtained by varying the ex-
perimental parameters, such as applied voltage, deposition time, and
concentration of the diamond nanoparticles in the suspension. All
fabricated layers were of homogeneous thickness, without macro-
scopic cracks or holes. Platinum clusters were electrochemically de-
posited from the aqueous solution of the precursor complex by the
step and sweep potential method. The results of the methanol
electro-oxidation study conducted by using platinum deposited onto
the electrophoretically deposited diamond nanoparticle layers
B835
Figure 10. Color online XPS showing the platinum presence in metallic
state on the electrophoretically deposited diamond nanoparticle electrode.
showed that the current was higher for the electrodes in which the
platinum deposition was carried out with a lesser number of elec-
trodeposition cycles. This might be due to the platinum nanoparticle
size; they tend to agglomerate as the number of platinum deposition
cycles increases. The present investigation shows that the stable
nondoped diamond thin film prepared by the electrophoretic method
can be employed to fabricate an electrode material. This methodol-
ogy may be applied for future boron-doped nanodiamond catalyst
support materials for fuel cell applications as well.
Acknowledgments
This research was supported in part by the NASA-URC grant no.
NNX08BA48A, NSF-EPSCoR Institute for Functional Nanomateri-
als grant no. OIA-0701525, and NSF NSEC Center for Hierarchical
Manufacturing grant no. CHM-CMMI-0531171. K.S. was a partici-
pant in the Scientific Research Program for Future Science and Math
Teachers sponsored by ALaCiMa, an NSF proposal grant no.
0314557. We thank Dr. Mark Prelas and his group for the PGNAA
analyses at the University of Missouri at Columbia.
University of Puerto Rico assisted in meeting the publication costs of this
article.
Figure 9. a EDX spectra showing the
platinum presence on the electrophoreti-
cally deposited diamond nanoparticles. b
The SEM picture shows various sizes of
the platinum particles.
B836 Journal of The Electrochemical Society, 157 6 B831-B836 2010
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