Journal of Electroanalytical Chemistry 633 (2009) 327–332

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Studies of the electrodeposition of platinum metal

from a hexachloroplatinic acid bath
Hartini M. Yasin, Guy Denuault, Derek Pletcher *
School of Chemistry, The University of Southampton, Southampton SO17 1BJ, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: The mechanism of platinum deposition onto carbon from a bath containing H2PtCl6 in 0.1 M HCl is dis-
Received 19 March 2009 cussed. Although voltammograms show multiple cathodic waves, it is shown that they all result from the
Received in revised form 23 June 2009 reduction of Pt(IV) to Pt(0) and there is no evidence for Pt(II) as a stable intermediate at any potential; the
Accepted 26 June 2009
multiple waves arise because the hexachloroplatinic acid exists in solution as a mixture of kinetically
Available online 1 July 2009
inert Cl/H2O complexes. The nucleation of the Pt centres on carbon is a very slow process even with
a large overpotential and this leads to surfaces with well dispersed hemispherical nuclei. Moreover, each
Keywords:
Pt centre appears to grow only to a limiting size before growth ceases.
Chloroplatinic acid
Pt electrodeposition
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction
The baths used in the commercial electroplating of platinum
have been reviewed [1–3]. Usually, the objective is the deposition
of a uniform, smooth and reflecting Pt layer and the common baths
are based on either Pt(II) or Pt(IV) complexes and require the
plating to be carried out at an elevated temperature (usually
333–363 K); some detailed studies of the mechanism of Pt(II)
reduction have previously been reported [4–6].
Within academic institutions, it has been more common to elec-
troplate platinum from solutions containing hexachloroplatinic
acid. Indeed, recent years have seen a number of papers using such
solutions for the electrodeposition of highly structured Pt deposits.
For example, such procedures have been used to form: (a) Pt
microparticles with small dimensions [7–16]; (b) arrays of Pt
microwires by deposition into a 10 lm thick, nuclepore polycar-
bonate membrane with 100 nm pores [17] or alumina membranes
with 200 nm pores [18]; (c) Pt foams with submicron dimensions
by deposition into self assembled structures of polystyrene micro-
spheres [19,20]; and (d) highly ordered, nanoporous Pt films by
deposition from hexagonal (H1) liquid crystal phases based on con-
centrated aqueous solutions of surfactants [21–24]. In addition,
several papers using chronamperometry and SEM have addressed
the nucleation and growth of Pt on to, for example, carbon [25],
diamond [26] and titanium [27].
Surprisingly, in view of this body of work, there have been few
2
systematic studies of the mechanism for the reduction of PtCl6 .
Over the years, several groups have reported voltammograms for
* Corresponding author. Tel.: +44 (0) 2380 593519.
E-mail address: dpl@soton.ac.uk (D. Pletcher).
2
solutions of PtCl6 with two or more reduction waves and inter-
preted the voltammograms as showing that the reduction proceeds
through the sequence Pt(IV) to Pt(II) to Pt metal [14,28–32]. Some
aspects of Pt deposition onto Pt and glassy carbon from H2PtCl6
have been the subject of detailed studies. Two papers [33,34]
report the importance of deposition conditions on the structure
of the deposit and highlight the inhibition of the deposition reac-
tion by chloride ion as well as proposing a deposition mechanism
involving the disproportionation of Pt(II).
2
This paper reports a further study of the reduction of PtCl6 in a
HCl electrolyte and focuses on the interpretation of the voltamme-
try of these solutions, demonstrating that two reduction waves do
not correspond simply to the reductions Pt(IV) to Pt(II) and Pt(II) to
Pt.
2. Experimental
All solutions were prepared with deionised water (Purite Select
water purifying system; resistivity >18 MX cm), hydrogen hexa-
chloroplatinate (IV) hydrate (Aldrich, 99.9%) and hydrochloric acid
(BDH, sp. gr. 1.18). All solutions were deoxygenated with argon
(BOC) and experiments were carried out at room temperature.
The electrochemical experiments were carried out using a three
electrode, two compartment glass cell. The working electrode was
either: (a) a 7 lm diameter carbon fibre dipped into the electrolyte
to the depth of 5 mm; (b) a 3 mm diameter glassy carbon rotating
disc electrode; or (c) a 3 mm diameter gold disc rotating disc. Un-
less otherwise stated, before each experiment, the disc electrode
was polished on a polishing wheel with silicon carbide CC-1200,
followed by alumina suspension of 5 lm, 0.3 lm and 0.05 lm
and then rinsed thoroughly with distilled water. The carbon fibres

0022-0728/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2009.06.020
328 H.M. Yasin et al. / Journal of Electroanalytical Chemistry 633 (2009) 327–332

were used only for one experiment before disposal. The fibres were E vs SC E / V
coated with Epofix Resin EPOF1 so that a 5 mm length was exposed -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6
0.0
to the electrolyte solution. The counter electrode was a platinum
mesh secondary electrode in the same solution as the working
electrode. The reference electrode was a saturated calomel elec- -0.5
trode (SCE) mounted inside a Luggin capillary. The experiments
were controlled using a micro Autolab Type III with the General

j / mA cm-2
Purpose Electrochemical System (GPES) version 4.9 (EcoChemie) -1.0
and data was analysed using standard software.
The images of the deposits were obtained with a Philips XL30
-1.5
ESEM environmental scanning electron microscope operating in
the wet mode with a secondary electron (SE) detector and fitted
with an EDAX International Phoenix 2 EDX. -2.0

3. Results
-2.5

Figs. 1 and 2 report voltammograms recorded at polished rotat-
ing vitreous carbon electrodes for an aqueous solution of 5 mM
H2PtCl6 + 0.1 M HCl. For Fig. 1, the negative potential limit was se-
lected to be 0.4 V vs. SCE, just negative to the potential where H2
evolution commences on a surface with a Pt deposit. It can be seen
that on the first potential scan towards more negative potentials,
there is no cathodic current positive to +0.15 V and there are
two reduction waves with half wave potentials at 0.08 V and
0.24 V vs. SCE. The waves overlap to some extent but it is clear
that the two waves have similar limiting current densities. The
back scan towards more positive potentials is quite different. On
this scan, there appear to be three overlapping reduction waves
and substantial cathodic current is observed at all potentials less
positive than +0.5 V vs. SCE. When a second scan is recorded
immediately after the first without repolishing the electrode, the
voltammogram now looks very similar to the reverse scan of the
first cycle; again, cathodic current is observed at all potentials neg-
ative to +0.5 V and three reduction waves are evident. Fig. 2 shows
the voltammetric response for the polished vitreous carbon disc
when the negative potential limit is restricted to 0.15 V, towards
the top of the first reduction wave. Again, there is strong hysteresis
between the forward and reverse scans with the current being
much higher on the reverse scan. As expected for a medium with
a relatively low chloride ion concentration, there is no anodic cur-
rent that can be associated with the anodic dissolution of the plat-
inum with either voltammogram. The characteristics of the
voltammograms of Figs. 1 and 2 are most commonly associated
Fig. 2. Voltammogram, first scan with a polished electrode, with a decreased
negative potential limit. Rotation rate 900 rpm. Other conditions as Fig. 1.
with systems that involve the nucleation and growth of a new
phase on the electrode surface. Hence, the voltammograms on
the reverse and second scans appear to be for the reduction of
2
PtCl6 at a newly formed Pt surface. In general, the hysteresis
could arise due to a change in the surface of the electrode resulting
from reduction but this explanation is unlikely here since there is
no evidence for the reduction of carbon oxides around +0.15 V and
almost identical voltammetry was recorded at a gold disc elec-
trode, see below.
Fig. 3 shows voltammograms recorded as a function of the rota-
tion rate for a vitreous carbon disc electrode already coated with Pt
so that features involving nucleation are avoided. At each rotation
rate, reduction commences at +0.6 V vs. SCE and three reduction
waves are observed, these being particularly well resolved with
the lowest rotation rate. The first wave is very drawn out along
the potential axis but still accounts for approximately half the cur-
rent observed at 0.35 V. It can also be seen that the limiting cur-
rent for the first wave, measured at +0.1 V is proportional to the
square root of the rotation rate – the first reduction reaction is
mass transport controlled with respect to a species in solution.
At 400 rpm, the second and third waves are steeper but they be-
come more drawn out with increasing rotation rate. Clearly, the
current at 0.35 V is strongly dependent on rotation rate but at
the higher rotation rates, the plateaux are poorly defined; while

E vs SCE / V
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 E vs SC E / V
0 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
0
-1
-2
-2
-4
-3 -6
a
j / mA cm -2

-4 -8
j / mA cm-2

-5 -10 b

-6 -12
c
-7 -14
-16
-8 d
-18
-9
-20
Fig. 1. Voltammograms recorded at a rotating vitreous carbon electrode for an
aqueous solution of 5 mM H2PtCl6 + 0.1 M HCl saturated with argon. Rotation rate Fig. 3. Voltammograms as a function of rotation rate using a vitreous carbon disc
400 rpm. Potential scan rate was 20 mV s1. — First scan on polished electrode — electrode with a Pt coating. Solution: 5 mM H2PtCl6 + 0.1 M HCl, Ar saturated.
second scan without polishing the electrode. The arrows indicate the direction of Potential scan rate 20 mV s1. (a) 400 rpm, (b) 900 rpm, (c) 1600 rpm, and (d)
scan. 2500 rpm.
 H.M. Yasin et al. / Journal of Electroanalytical Chemistry 633 (2009) 327–332
the current at this potential is probably also mass transport con-
trolled, this cannot be confirmed with certainty from the variation
of current density with rotation rate. Certainly, the current density
at 0.35 V is compatible with the mass transport controlled, 4e
reduction of all the Pt(IV) in solution estimated via the Levich
equation.
Experiments with a Au disc electrode led to voltammograms
with the same general characteristics although the half wave
potentials for the reduction processes on the first scan (+0.05 V
and 0.15 V vs. SCE) were shifted positive showing that nucleation
of the Pt phase is faster on gold. During experiments with both vit-
reous carbon and gold disc electrodes, it was very clear that the
above responses during the initial cycles were dependent on the
complete removal of Pt metal from the surface. Moreover, com-
plete removal was difficult to achieve and required extensive pol-
ishing of the surface; the Pt nuclei adhere well to both carbon and
gold. Hence, it was desirable to use a ‘disposable’ surface and fur-
ther experiments were therefore carried out with 7 lm carbon fi-
bre electrodes, length 5 mm, and these were used only for one
experiment. The voltammetry of the solution of 5 mM
H2PtCl6 + 0.1 M HCl at the carbon fibre electrodes was again very
similar to that at the vitreous carbon disc electrode discussed
above.
The deposition of mesoporous Pt films in Southampton [21–24]
has generally employed a liquid crystal medium where the aque-
ous phase contains H2PtCl6 but no other electrolyte. It was there-
fore of interest to investigate the voltammetry of 5 mM H2PtCl6
without the addition of HCl and this becomes feasible using the
microelectrodes. Fig. 4 reports the first and second scan cyclic vol-
tammograms for the aqueous solution of 5 mM H2PtCl6. Again, it
can be seen that the voltammograms are very similar to those re-
ported in the presence of 0.1 M HCl. On the first cycle, nucleation of
the Pt centres seems more difficult and significant cathodic current
is not seen until negative to 0.2 V but the reverse scan clearly
shows three cathodic waves and cathodic current continues to
+0.6 V. The second cycle follows the reverse scan of the first cycle
with cathodic current occurring at all potentials negative to +0.6 V;
the most negative cathodic wave shows an increase in height and
this may result from a larger contribution from hydrogen adsorp-
tion on the growing Pt surface.
-2
-4
-6
-8
j / mA cm-2
-10
-12
-14
-16
-18
-20
-0.4
Fig. 4. Two consecutive cyclic voltammograms recorded on 7 lm diameter (l = 5 mm) carbon fibre in aqueous 5 mM H2PtCl6 (without HCl) degassed with Ar at a scan rate of
20 mV s1. (a) First scan and (b) second scan.
329
Hence, the voltammetry is consistent with all the cathodic
waves resulting from the reduction of Pt(IV) to Pt metal; if Pt(II)
is formed, it is unstable under the conditions of the experiments.
All the voltammograms at the rotating disc and fibre electrodes
also imply that the nucleation of a Pt metal phase is a difficult pro-
cess requiring a large overpotential. This was studied further using
a potential step technique with carbon fibre electrodes (a fresh, un-
used length of fibre was used for each experiment); Fig. 5 shows
the transient response to a step from +600 mV to a series of nega-
tive potentials. It can be seen that well formed rising transients are
observed consistent with nucleation and growth of a new phase.
The timescale of the rising transients are, however, unusually long.
Even at 0.25 V, the increase in current occurs over 300 s. This po-
tential is in the limiting current plateau region of the most negative
wave in the voltammograms and 750 mV negative to where depo-
sition appears to occur on the back scan of the voltammograms, see
Fig. 1 or at a surface with Pt already deposited, see Fig. 3. On the
other hand, the limiting current density at this rather negative po-
tential is similar to that expected when the rate of reduction is con-
trolled by diffusion of the Pt(IV) in solution to a microcylindrical
electrode [31]. It can also be noted that the change in the timescale
of the rising transients is surprisingly insensitive to the applied po-
tential; this indicates that the kinetics of nucleation and growth is
insensitive to changes in potential over the potential range 0.1 V
to 0.25 V. We were also interested as to whether nucleation could
be induced at positive potentials. At +0.1 V vs. SCE, some increase
in current was observed on a 1800 s timescale. At +0.2 V, no rise
in current was seen even when the electrode was monitored for
3 h; nucleation does not occur at +0.2 V or more positive
potentials.
Clearly, the most definitive confirmation that all the cathodic
current negative to +0.5 V is due to reduction of Pt(IV) to Pt metal
would be to demonstrate that Pt deposition can occur at more po-
sitive potentials following creation of Pt centres. The potential se-
lected for such experiments were +0.2 V, chosen because it had
already been demonstrated that nucleation of Pt centres does not
occur while the first reduction wave is mass transfer controlled
at this potential. Hence, a number of double potential step experi-
ments were carried out. The potential was stepped from +0.6 V vs.
SCE to 0.25 V for several periods of time and then to +0.2 V and
a
b
-0.2 0.0 0.2 0.4 0.6
E vs SCE / V
330 H.M. Yasin et al. / Journal of Electroanalytical Chemistry 633 (2009) 327–332

0
0V
-2 -0.05 V

-4

-6

-8
j / mA cm -2

-0.10 V
-10

-12
-0.125 V
-14
-0.20 V
-16

-18 -0.25 V
-20
0 50 100 150 200 250 300
time / s

Fig. 5. Current vs. time transients in response to steps from +600 mV vs. SCE to the potentials indicated on the figure. Each transient recorded at a new carbon fibre electrode.
Solution: 5 mM H2PtCl6 + 0.1 M HCl saturated with argon.

this value was maintained until the total cathodic charge during
the two pulses was ten times that during the first pulse. The cur-
rent versus time response to these experiments are shown in
Fig. 6. As expected, during the first pulse a rising cathodic transient
was observed (and this was highly reproducible). After switching
the potential to +0.2 V, almost constant currents were observed
after an initial rise. It can be seen that for shorter periods at
0.25 V, the constant current during the second pulse becomes lar-
ger with the length of the first pulse reflecting an increased num-
ber of nuclei with time formed during this first pulse. When the
period at 0.25 V reaches 80 s, the number of nuclei becomes inde-
pendent of the length of the first pulse – nuclei are formed at all
the sites where nucleation is possible. Again, this is a surprisingly
long period necessary to saturate the surface sites available for
nucleation. It can also be seen that with the longer first pulses,
the constant current during the second pulse is 5 lA and this
compares with a steady state current of 20lA if the potential
is held at 0.25 V. This ratio of currents is similar to that seen on
the voltammograms for a Pt activated vitreous carbon disc
electrode.
Fig. 7 shows typical SEM images of the carbon fibre electrodes
after the single (Fig. 7a and c) and double potential step experi-
ments (Fig. 7b and d). The clearest conclusion from visual observa-
tion of the images is that further deposition of Pt occurs during the
second step at +0.2 V. The increase in surface area of Pt can also be
confirmed by: (a) recording the cyclic voltammetry of the elec-
trodes in 1 M H2SO4 and comparing the charges for hydrogen
adsorption or platinum oxide reduction, (b) monitoring the current
for H2 evolution from the sulphuric acid solution at 0.5 V or (c)
recording voltammograms for O2 reduction in 0.5 M HClO4 and

0
a
b
-2

-4 c
e
d
-6
-2
j / mA cm

-8

-10

-12

-14

0 500 1000 1500 2000 2500 3000

time / s

Fig. 6. Current time response from double potential step experiments, +0.6 V vs. SCE to 0.25 V to +0.2 V until the total cathodic charge was 10 times that during the pulse at
0.25 V. The period at 0.25 V was (a) 20 s (charge passed 0.12 mC cm2), (b) 40 s (0.37 mC cm2), (c) 60 s (0.63 mC cm2), (d) 80 s (1.04 mC cm2), and (e) 100 s
(1.38 mC cm2). Each response recorded at a new carbon fibre electrode. Solution: 5 mM H2PtCl6 + 0.1 M HCl saturated with argon.
 H.M. Yasin et al. / Journal of Electroanalytical Chemistry 633 (2009) 327–332 331

Fig. 7. SEM image of the carbon fibre after (a) a single potential step experiments from +0.6 V to 0.25 V for 20 s, (b) a double potential step from +0.6 V to  0.25 V (20 s, 0.12
mC cm2) to +0.2 V (1.2 mC cm2), (c) a single potential step experiments from +0.6 V to 0.25 V for 60 s, and (d) a double potential step from +0.6 V to 0.25 V (60 s,
0.63 mC cm2) to +0.2 V (6.3 mC cm2). Carbon fibre electrode. Solution: 5 mM H2PtCl6 + 0.1 M HCl saturated with argon.

comparing the currents in the foot of the cathodic wave. The iment; deposition of Pt metal occurs at +0.2 V vs. SCE. The form
images, however, disclose a number of other facts about the depo- of the voltammetry is fully explained by slow nucleation of Pt
sition of Pt onto the carbon. Firstly, the Pt deposits as approxi- centres and the reduction of Pt(IV) to Pt metal without Pt(II)
mately hemispherical centres. As expected, the number of visible as a stable intermediate. The earlier literature proposing that
centres increases with time at 0.25 V. Secondly, we were unable the first reduction wave is due to the reduction of Pt(IV) to Pt(II)
to form complete layers of Pt over the whole surface; growth was [14,28–32] is incorrect.
limited to particular sites and the hemispherical centres seemed The speciation of hexachloroplatinic acid in aqueous chloride
unable to grow beyond a critical size. Thirdly, it is very clear that solutions has been studied by both UV–visible spectroscopy
the number of visible centres increases substantially during the [35,36] and 195Pt NMR [37,38]. Although the exact ratio of the spe-
2
second step at +0.2 V. Since it has been shown that nucleation is cies depends on the concentrations of PtCl6 and Cl, pH and tem-
impossible at this potential, it must be concluded that at the end perature, under the conditions of the voltammetry reported in this
of the first pulse there are a number of Pt nuclei, too small to be paper it is to be expected that the solution will contain substantial
2
visible by the electron microscope. In principle, the size and num- amounts of three, kinetically inert complexes, PtCl6 and two spe-
ber density of Pt centres observed by SEM could be used to esti- cies resulting from the hydrolysis reactions
mate the weight of Pt deposited and hence the current efficiency
for Pt deposition. While it is clear that Pt deposition is the major
reaction at +0.2 V, the accuracy of estimating nuclei dimensions
and number density from the SEM is not good enough for a quan-
titative calculation. High resolution SEM also showed that the Pt
nuclei are composed of a large number of small crystallites as pre-
viously reported [34].
Fig. 8 reports a typical SEM image for a platinum deposit onto a
vitreous carbon disc electrode. It can be seen that again the Pt is
deposited as isolated and rather well separated centres. The depos-
its reported above do not result from the fibres having unusual sur-
face characteristics for carbon.

4. Discussion

The observation of extended ‘nucleation loops’ on all cyclic

voltammograms, even when the negative potential limit only in-
cludes the first cathodic wave, strongly implies that all the
cathodic waves lead to the deposition of platinum metal. This
conclusion is reinforced by the difference between the first and Fig. 8. SEM image of the surface of a 3 mm diameter vitreous carbon RDE after
second cycles of voltammograms. The conclusive evidence is, deposition of Pt from 5 mM H2PtCl6 in 0.1 M HCl, Ar saturated. Potential step from
however, the SEM images after the double potential step exper- +0.6 V to 0.16 V vs. SCE for 100 s.
332 H.M. Yasin et al. / Journal of Electroanalytical Chemistry 633 (2009) 327–332
2 
PtCl6 þ H2 O ¢ PtCl5 ðH2 OÞ þ Cl

PtCl5 ðH2 OÞ þ H2 O ¢ PtCl5 ðH2 OÞ2 þ Cl

Any interpretation of the voltammetry must take into account
this speciation of the solution.
Reduction of each complex is to be expected and the multiple
cathodic waves would be observed if each complex underwent
the reaction

PtðIVÞ þ 4e ! Pt
2
The potentials for the reduction of PtCl6 ,PtCl5(H2O) and
PtCl5(H2O)2 will be different. While Pt(II) may be formed, it is not
stable in the conditions of the experiments. One possibility is that
the Pt(II) immediately undergoes further reduction. Petrii et al.
[33] favour a mechanism whereby the Pt metal arises by dispro-
portionation of Pt(II). This cannot be ruled out but the voltammetry
observed would require that the disproportionation occurs for all
Pt(II) species resulting from the reduction of the three Pt(IV) com-
plexes and that each is rapid since the waves are mass transfer
controlled. The voltammograms would imply an approximate ratio
2
of PtCl6 :PtCl5(H2O):PtCl5(H2O)2 of 10:3:7 in 0.1 M HCl.
Perhaps the most unusual characteristic of this system is the
form of the metal deposit on the carbon surface. The platinum
grows as isolated, ‘hemispherical’ centres; it appears that nuclei
only form at specific sites on the carbon surface and, even at these
sites, a large overpotential is always required to drive nucleation.
Moreover, it appears that the centres do not grow beyond a critical
size thereby making it difficult to form complete, uniform layers.
Also the kinetics of nucleation (as indicated by the timescales of
the rising transients) show an unusually low dependence on the
applied potential as well as requiring a high overpotential. Petrii
et al. [33] attribute the slow nucleation of Pt from these solutions
to adsorption of chloride ion onto the substrate surface. The slow
nucleation is, however, surprising since the Pt deposit does not dis-
solve in the 0.1 M HCl electrolyte and this would imply that, even
with small nuclei, the re-dissolution of the Pt atoms will not be as
facile as with some other metals. The behaviour suggests a com-
plex mechanism for formation of the initial Pt atoms in the nuclei
and a role for Pt(II) and disproportion cannot be ruled out [29]. If,
however, it does have a role, the reduction of Pt(II) to Pt(0) is al-
ways rapid compared to the reduction of Pt(IV) to Pt(II) on the
growing nuclei.
Isolated hemispherical centres of Pt were also observed when
electrodeposition onto a vitreous carbon disc. Hence, the form of
the deposit is not determined by a property of the carbon fibre. In-
deed, earlier papers [25,33,34] also showed similar deposits on
glassy carbon although their carbon surface appears to have many
more active nucleation sites; the same paper also report a strong
dependence of the deposit structure on the substrate. It is interest-
ð1Þ ing to speculate on the generality of the nucleation and growth
ð2Þ properties observed here. For example, they may be critical in
determining the structure of the Pt/carbon powder surfaces so
widely used as fuel cell electrocatalysts.
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