Electrocatalysis (2015) 6:447454
DOI 10.1007/s12678-015-0261-2
ORIGINAL RESEARCH
Kinetic Investigations of Glycerol Oxidation Reaction on Ni/C
V. L. Oliveira 1,2 & C. Morais 2 & K. Servat 2 & T. W. Napporn 2 &
P. Olivi 3 & K. B. Kokoh 2 & G. Tremiliosi-Filho 1
Published online: 5 June 2015
# Springer Science+Business Media New York 2015
Abstract This study evaluates the electrochemical oxidation
of glycerol using a nickel-supported catalyst under several
well-defined experimental conditions. The influence of scan
rate, temperature, glycerol, and NaOH concentrations were
systematically investigated. The slope of the log-log relation-
ship of the anodic peak current for glycerol oxidation as a
function of the scan rate indicates that the electrochemical
glycerol oxidation is a complex mechanism partially limited
by diffusion-controlled process. This is in agreement with the
temperature effect on glycerol oxidation, since the slope value
associated with the relationship between the logarithm of the
current density of the anodic peak and the inverse of temper-
ature also indicates a diffusion process. When the glycerol
concentration increases, the peak associated to its oxidation
also increases, but it seems to reach a limit. This behavior was
associated with two main effects, i.e., the saturation of the
active catalytic sites on the electrode surface and the change
in the glycerol oxidation mechanism as demonstrated by FTIR
spectroscopic measurements.
* K. B. Kokoh
boniface.kokoh@univ-poitiers.fr
* G. Tremiliosi-Filho
germano@iqsc.usp.br
1
Instituto de Qumica de So Carlos, Universidade de So Paulo,
C.P. 780, 13560-970 So Carlos, SP, Brazil
2
Universit de Poitiers, IC2MP UMR CNRS 7285, 4 rue Michel
Brunet B27, TSA 51106, 86073 Poitiers cedex 09, France
3
Departamento de Qumica, Faculdade de Filosofia Cincias e Letras
de Ribeiro Preto, Universidade de So Paulo, 14040-901 Ribeiro
Preto, SP, Brazil
Keywords Kinetic data . Glycerol electrooxidation . Nickel .
Infrared spectroscopy
Introduction
The electrochemical oxidation of molecules on non-noble d-
block metals, such as iron, nickel, and cobalt, is of high impor-
tance due to their numerous applications [1]. The nickel catalyst
presents high activity, low cost availability, outstanding anti-
poison ability, and simplicity of preparation and has demonstrat-
ed long-term stability in strongly alkaline environments [24].
Nickel-based electrode materials have received considerable
attention over the three last decades in several applications, such
as alkaline batteries [5], fuel cells [6], capacitors [7], sensors [8],
and catalysts for various electrochemical reactions [24, 916].
In all of these processes, the nickel surface state impacts its
performance, the catalytic activity, and efficiency. At lower po-
tential values, metallic nickel is oxidized to Ni(OH)2 in alkaline
solutions. In the higher electrode potential domain, Ni(OH)2
transforms into NiOOH as the highest Ni oxidation state which
is found to be a good catalyst for alcohol oxidation [1, 3, 11, 15].
Glycerol is a non-toxic polyol, being soluble in water which
makes its storage and retrofit potentially far easier. It displays a
relatively high theoretical energy density (~6.4 kWh L1) [17,
18]. The oxidative conversion of this molecule to more valued
chemicals does not only improve, in economic terms, the bio-
diesel production but also reduces environmental impact of this
process [1925]. Since many oxidation products can be
formed, the control of the selectivity by carefully designed
electrocatalysts is required. Pt catalysts present high selectiv-
ities to dihydroxyacetone [12, 2527], while glyceraldehyde
[28] and hydroxypyruvic acid [29] were obtained on PtBi cat-
alysts by controlling the reaction conditions and, particularly,
the electrolytic solution pH value. Glycerate, mesoxalate,
448
glycolate, tartronate, oxalate, and formate ions are reported as
the main products observed during the glycerol oxidation reac-
tion in alkaline medium on noble electrodes [9, 17, 20, 23, 25,
3032]. These products are potentially valuable chelating
agents, which can be also used as intermediate compounds
for the synthesis of fine chemicals and polymers [3335].
In previous works [9, 36], we have shown that free-noble
metal materials could be used as catalysts for glycerol oxida-
tion. Using a combination of in situ Fourier transform infrared
(FTIR) spectroscopy and high-performance liquid chromatog-
raphy (HPLC), it was demonstrated that at 1.6 V, formate is
the main product and glycolate and glycerate are detected as
minor products. In this work, complementary electrochemical
investigations are proposed to determine fundamental aspects
of the reactivity of glycerol on nickel catalysts under a range
of well-controlled experimental conditions including temper-
ature, scan rate, NaOH, and glycerol concentrations. Addi-
tionally, spectroscopy measurements in several glycerol con-
centrations were performed in order to investigate the reaction
mechanism at different glycerol concentrations.
Experimental
Synthesis of Carbon-Supported Ni
by Impregnation-Reduction Method
Carbon-supported nickel, Ni/C, was prepared by a controlled
impregnation-reduction method described elsewhere [37, 38].
A suitable amount of carbon Vulcan XC-72 is mixed with
Ni(NO 3 ) 2 6H 2 O (Aldrich P.A.) and ultrapure water
(Millipore-MilliQ water with a resistivity of 18.2 M cm
at 20 C) to obtain an expected metal loading of 20 wt%.
The mixture was sonicated for 1 h. After heating at 80 C to
evaporate water, the resulting residue was ground to a fine
powder. A heat treatment was conducted in a tubular oven
under argon atmosphere at 100 C for the complete elimina-
tion of water, followed by a treatment under H2 atmosphere at
300 C with a temperature increase rate of 5 C min1. Vulcan
XC 72 carbon black (CABOT, specific area of 250 m2 g1),
used as substrate for Ni dispersion, was previously treated
under argon atmosphere at 850 C for 5 h.
Electrochemical Measurements
The solutions were prepared from NaOH (Sigma-Aldrich
97 %), Glycerol (Sigma-Aldrich99 %), and ultrapure water.
Electrochemical experiments were carried out in a 0.10 mol L1
NaOH supporting electrolyte. The electrolytic solution was
deaerated by purging with argon for 30 min. During the exper-
iments, an argon stream was maintained over the electrolyte.
The voltammetric measurements were performed with an
AUTOLAB model PGSTAT-30 potentiostat in an undivided
Electrocatalysis (2015) 6:447454
three-electrode Pyrex cell. The cell allowed also the tempera-
ture control that was considered in the present study. A revers-
ible hydrogen electrode (RHE) and a large surface area of a
platinum plate were used as reference and counter electrode,
respectively. All potentials are reported with respect to RHE.
The working electrode consisted of catalytic powders depos-
ited onto a fresh polished glassy carbon with a geometric
surface area of 0.385 cm2.
Spectroscopic Experiments
In situ FTIR measurements were carried out in a Bruker IFS
66v spectrometer as described in the literature [36]. In this
work, several glycerol concentrations were employed ranging
from 5 to 100 mmol L1 in order to promote insights about
mechanistic aspects. In the chronoamperometry/FTIRS exper-
iments, spectra were collected every 5 min for 2 h, with the
electrode potential set at 1.500.01 V versus RHE.
Results and Discussion
Cyclic Voltammetry of the Catalysts in the Absence
and Presence of Glycerol
Cyclic voltammetry (CV) was used in order to examine the
electrochemical properties of Ni/C catalyst in alkaline solu-
tions. The surface oxidation of nickel in alkaline media is well
known [39] and presents two or more steps that could be
illustrated by the following equations:
(i) The first step is the oxidation of Ni0 to -Ni(OH)2 at
lower potentials (0.00E0.50 V vs. RHE):
Ni0 2 OH NiOH2 2e 1
(ii) With the increase in the potential, 0.50E1.40 V ver-
sus RHE, the -form species could be transformed into a
less hydrated and more stable phase -Ni(OH)2 (Eq. 2).
The direct oxidation of Ni0 to Ni(OH)2 is also possible
(Eq. 3):
NiOH2 NiOH2 2
Ni0 2 OH NiOH2 2e 3
Since the -phase of Ni(OH)2 is the most stable and ther-
modynamically favored Ni hydroxide phase, redox waves for
the Ni(II)/Ni(0) and /-phase Ni(OH)2 transformation are
not usually observed. Thus, the -Ni hydroxide form of Ni
hydroxide accumulates on the surface [1, 8, 16].
(iii) At more positive potential values, E>1.40 V ver-
sus RHE, -Ni(OH)2 could be oxidized to oxy-
Electrocatalysis (2015) 6:447454
hydroxide -NiOOH, while this latter species is
reduced at 1.30 V versus RHE during the negative
potential scan:
NiOH2 HO NiOOH H2 O e 4 potential region. This statement is in fair line with the previous
These processes can be seen in the cyclic voltammograms
presented in Fig. 1 in the absence of glycerol (black lines)
where the anodic and cathodic peaks can be easily observed.
In addition, NiOOH was reported to be the electrochemically
active phase toward the organics oxidation [2, 8, 9, 15, 16].
An increase in the anodic current is observed when glycerol
is present in the electrolytic solution (red line, Fig. 1a) at
~1.300.01 V. Furthermore, the glycerol oxidation potential
shifts to less positive values at more concentrated solutions
(Fig. 1b) what can be associated with the dependence of the
beginning of glycerol oxidation with the preliminary steps of
the transformation of -Ni(OH)2 into -NiOOH. As can be
noticed in Fig. 1b, the glycerol oxidation occurs just before the
Fig. 1 Voltammograms of the Ni/C electrode in 0.1 mol L1 NaOH
recorded at 5 mV s1 in the absence (black line) and the presence of
glycerol (red line). a 0.1 mol L1 glycerol, b 0.005 mol L1 glycerol
(Color figure online)
449
peak attributed to NiOOH, well known as the active catalytic
form. This phenomenon might be explained by the beginning
of the formation of oxy-hydroxide species which result from
the oxidation of Ni(OH)2 at the surface of the catalyst in this
infrared spectroscopy results which showed the formation of
formate in this potential region [9]. The oxygen evolution
reaction (OER) starts at ~1.500.01 V versus RHE in the
absence of glycerol and shifts toward more positive potentials
(1.9 V) in the presence of the organic molecule. This may be
due to a high adsorption affinity of elevated valence Ni species
with glycerol than with hydroxyl species (OH) [8, 39].
These results indicate that the Ni/C electrode material can
catalyze the glycerol electrooxidation due to the increase of
the oxidation state of nickel from +2 to +3 through the oxida-
tion of -Ni(OH)2 to nickel oxyhydroxide and the subsequent
glycerol electrooxidation at the -NiOOH surface. It is worthy
of note that, besides glycerol, nickel oxyhydroxide is also
consumed during the oxidation reaction with the formation
of -Ni(OH)2. This behavior is indicated by the absence of
the cathodic peak during the negative potential scan. None-
theless, the complete oxidation of glycerol to CO2 is very
difficult and many intermediates/products may be formed.
The intermediates and final products detected by HPLC in
the course of cumulative glycerol oxidation in alkaline medi-
um on nickel electrode are formate, as a main product, and
glycolate and glycerate as minor products, under the condi-
tions of 1.600.01 V versus RHE and 0.1 mol L1 NaOH
containing 0.1 mol L1 glycerol [36]. Under the same exper-
imental conditions, non-cumulative in situ FTIR experiments
were performed and only formate was observed [36, 42].
Effect of CV Scan Rate
The effects of potential scan rate on the Ni oxide species
formation as well as the glycerol oxidation on a Ni/C catalyst
were investigated in order to gain further insight into this
process dependence.
Tehrani et al. [40] studied the cyclic voltammograms of the
nickel electrode and observed that an increase in the scan rate
affects the -Ni(OH)2/-NiOOH peak which becomes pro-
gressively larger. Additionally, the value of the anodic peak
potential, Epa, also shifts to more positive potentials, probably
due to the early conversion of -Ni(OH)2 into -NiOOH and
the necessity of larger amount of Ni oxides to oxidize the
electrode surface at higher scan rates. Subsequently, the ca-
thodic peak potential, Epc, shifts negatively, probably because
of the uncompensated ohmic drop generated at high current
values and/or the reduction of more -NiOOH layers formed
during the positive potential going scan [8, 15, 16, 40].
Figure 2 represents the voltammograms of a Ni/C electrode
in 0.1 mol L1 NaOH containing 5 mmol L1 glycerol. The
voltammograms were recorded at different scan rates from 2
450 Electrocatalysis (2015) 6:447454

Fig. 3 Log-log plots of anodic peak current versus potential scan rate (v)
Fig. 2 Voltammograms of the Ni/C electrode in 0.1 mol L1 NaOH
for the glycerol oxidation in 0.1 mol L1 NaOH in the presence of
containing 0.005 mol L1 glycerol, collected at various scan rate values
0.005 mol L1 glycerol (red line) and 0.1 mol L1 glycerol (blue line).
at 20 C. Black line, 2 mV s1; red line, 5 mV s1; light blue line,
Inset: log-log plot of anodic peak current for -NiOOH formation versus
10 mV s1; blue-green line, 20 mV s1; pink line, 30 mV s1; yellow-
v, in 0.1 mol L1 NaOH in the absence of glycerol (Color figure online)
green line, 40 mV s1; and dark blue line, 50 mV s1 (Color figure online)

to 50 mV s1. The oxidation peak shifts toward higher poten- the result of the thermal activation of the glycerol oxidation in
tial values probably due, as pointed out above, to the irrevers- the electrode-solution interface on the -NiOOH catalytic lay-
ible renovation of the electrode surface related to the ohmic er. The apparent activation energy can be obtained through the
resistance at high current densities. The cathodic peak in- Arrhenius equation [42, 43]:
creases with the scan rate. This could imply that the higher 2 3
the scan rate is, the faster the electrochemical reaction of con- 6 dlog jp 7
version of -Ni(OH)2 into -NiOOH occurs. However, the E a 2:303R6
4
1 5
7 5
chemical reaction between oxyhydroxide and glycerol does d

not occur completely and, therefore, some oxyhydroxide
(NiOOH) species that remain on the surface could be electro- Figure 4b shows the plot of the logarithm of the peak cur-
chemically transformed into nickel hydroxide (-Ni(OH)2) rent density of glycerol oxidation versus the inverse of tem-
during the negative potential scan. Thus, the faster the scan perature. The apparent activation energy (Ea) obtained on Ni/
rate is, the more nickel hydroxide is electrochemically formed. C is 20.4 kJ mol1. This low value is typical of a limited mass
The log-log relationship of the anodic peak current as a
function of the scan rate is shown in Fig. 3. Slopes of 0.30
and 0.34 were obtained for 100 and 5 mmol L1 glycerol con-
centrations, respectively, indicating that despite increasing 20
times the concentration of the glycerol, the electrochemical pro-
cess remains very similar. Furthermore, the slopes suggest that
the glycerol oxidation is a complex mechanism, which is close
to a diffusion-controlled process, but it is not a pure diffusion-
controlled one. Additionally, the inset in Fig. 3 indicates that in
the presence of electrolyte support without glycerol, the process
is pure diffusion-controlled with a slope of 0.56 [41].

Effect of Temperature

The effect of temperature on the glycerol oxidation was stud-

ied in the range of 275 and 313 K. Figure 4a shows the cyclic
voltammograms of the glycerol oxidation at different temper-
atures on Ni/C catalyst in 0.1 mol L1 NaOH and 0.1 mol L1
glycerol at 5 mV s1. When the temperature is raised, a sig-
nificant increase in the peak current, jp, was observed. This is
Fig. 4 Voltammograms of the Ni/C electrode material recorded at
5 mV s1 in 0.1 mol L1 NaOH containing 0.1 mol L1 glycerol collected
at several T values ranging from 2 to 40 C. b Inset: plots of log jp versus
T1. Black line, 2 C; red line, 5 C; green line, 10 C; pink line, 20 C;
and blue line, 40 C (Color figure online)
Electrocatalysis (2015) 6:447454 451

transport reaction [41], which is in agreement with the scan

rate effect discussed in the previous section. Accordingly, it
can be concluded that the overall reaction process of glycerol
electrooxidation is limited not only by diffusion but also by
the rate of -Ni(OH)2 conversion into -NiOOH.

Effect of NaOH Concentration

From the findings of this work, it is assumed that the catalytic

glycerol oxidation reaction takes place at the surface of
oxyhydroxide formed at the expenses of nickel hydroxide. In
order to analyze the effect of changes in NaOH concentration
on the glycerol oxidation, a series of experiments with different
[OH] values were performed. Figure 5 represents the cyclic
voltammetric curves recorded at quasi steady state conditions
(5 mV s1) in various NaOH concentrations ranging from 0.1 to
0.75 mol L1 in the presence of 0.1 mol L1 glycerol.
The increase of the OH concentration has a significant ef-
fect on the glycerol oxidation as can be observed in the changes
of the peak potential (Ep) and peak current density (jp). The
onset potential shifts toward lower potential values, while the
current densities become higher and higher with the increment
of the NaOH concentration. The inset of Fig. 5 shows a linear
enhancement of jp as a function of the NaOH concentration.
These observed behaviors infer that the electrode surface is not
inhibited by the augmentation of NaOH concentration.
Effect of Glycerol Concentration
Cyclic Voltammetric Studies
Fig. 6 a Voltammograms of the Ni/C electrode material in 0.1 mol L1
NaOH containing various concentrations of glycerol: yellow-green line,
5 mmol L1; black line, 10 mmol L1; red line, 25 mmol L1; blue line,
50 mmol L1; and blue-green line, 100 mmol L1. v=5 mV s1. Insets: b
plot of anodic peak potential versus [glycerol]; c plot of anodic peak
current versus [glycerol] (Color figure online)
containing different glycerol concentrations ranging from 5
to 100 mmol L1 and recorded at a scan rate of 5 mV s1.
As can be noticed in Fig. 6a, the glycerol oxidation starts at
~1.300.01 V versus RHE, i.e., at the same potential region
where Ni(OH)2 is converting into NiOOH. When increasing
the glycerol concentration, an anodic overpotential takes place
and prevents the oxygen evolution reaction occurring. For this
reason, the upper potential limit was thereby increased toward
higher electrode potential values.

Cyclic voltammetric curves of the glycerol oxidation on Ni/C

material were recorded in 0.1 mol L 1 NaOH solution

Fig. 5 Voltammograms of the Ni/C electrode material recorded at

5 mV s1 in the presence of 0.1 mol L1 glycerol, collected at different
NaOH concentrations: black line, 0.1 mol L1; red line, 0.5 mol L1; pink Fig. 7 In situ FTIR spectra of the glycerol oxidation at 1.500.01 V
line, 0.6 mol L1; and blue line, 0.75 mol L1. Inset shows the plots of versus RHE on a Ni/C electrode in 0.1 mol L1 NaOH containing several
anodic peak current density versus [NaOH] (Color figure online) glycerol concentrations
452
The plots of Ep and jp versus glycerol concentration show a
deviation from linearity (Fig. 6b, c) for a glycerol/NaOH ratio
over 1:5, i.e., at glycerol concentrations above 20 mmol L1.
This could be due to the saturation of the NiOOH surface
catalytic sites by an excessive glycerol amount. Such electro-
chemical behavior was already observed in the oxidation of
acetyl salicylic acid [11] and isopropanol [16] on a nickel
electrode surface. Another possible reason is a change in the
reaction order due to the modification of the reaction mecha-
nism. This aspect can be clarified by the in situ FTIR spec-
troscopy measurements.
In Situ FTIR Spectroelectrochemical Experiments
In situ infrared reflectance spectroscopy was employed in order
to determine the reaction intermediates and products issued
from the glycerol oxidation on the Ni/C catalyst in
0.1 mol L1 NaOH and several glycerol concentrations
(Fig. 7). The bands corresponding to the different products
were attributed by comparison with references of expected
Fig. 8 In situ FTIR spectra of the
glycerol oxidation on a Ni/C
electrode at 1.500.01 V versus
RHE in 0.1 mol L1 NaOH con-
taining several concentrations.
Beginning of the potential polari-
zation (red line), and after 5 min
(blue line), 1 h (pink line), and 2 h
(black line) of polarization (Color
figure online)
Electrocatalysis (2015) 6:447454
compounds. At highest glycerol concentrations, 0.05 and
0.10 mol L1, three bands centered at 1351, 1385, and
1575 cm1 can be seen; they are assigned to formate, making
it the sole detectable product. The small positive bands found at
1113 and 1045 cm1 are attributed to the glycerol consumption
that is clearer at these high concentrations [45]. At the smallest
employed concentrations, the formate bands could not be seen.
However, in those conditions, several other bands were detect-
ed. The band located at 1245 cm1 may be attributed to the C
O stretch of carboxylic acids [17, 20, 36]. A large band centered
at 1390 cm1 is also present at the smallest glycerol concentra-
tions and is attributed to the presence of carbonate that results in
the thorough glycerol oxidation to carbon dioxide which inter-
acts with hydroxyl to give carbonate. In addition, the band at
1160 cm1 is assigned to glycolate [30, 31, 36, 44]. According
to the literature, a band at 1350 cm1 was also expected for this
species, but the large intensity of the carbonate band at
1390 cm 1 may overlap this one. Finally, the band at
1650 cm1 could be due the HOH bending from interfacial
water present inside the thin layer [30].
Electrocatalysis (2015) 6:447454
As can be seen in Fig. 7, the bands of the reaction products
are not the same for all concentrations at 1.500.01 V versus
RHE. These results are in agreement with cyclic voltammetry
results for which above 20 mmol L1 glycerol, the curve slope
indicated a mechanism change (Fig. 6b). Therefore, if lower
glycerol concentration was considered (10 and 5 mmol L1),
the process changes because the reaction mechanism changes
and other products reactions can be observed. As conclusive
remark, voltammetric (Fig. 6a) and in situ FTIR data (Fig. 7)
indicate that the kinetics and the reaction mechanism of the
glycerol oxidation are relatively different depending on the
glycerol concentration.
In situ FTIR spectra of 5, 10, 50, and 100 mmol L1 glyc-
erol in 0.1 mol L1 NaOH solutions at the beginning and after
2 h of polarization at 1.500.01 V and on Ni/C are compared
in Fig. 8. These results show that at the beginning of polari-
zation, the bands are practically the same indicating the for-
mation of formate as the main product (bands at 1578, 1385,
and 1351 cm1). Meanwhile, after long polarization time, the
main products found for the lowest glycerol concentrations are
carbonate (band at 1390 cm1) and oxalate (bands at 1245,
1620, and 1159 cm1). Therefore, this confirms that the glyc-
erol oxidation mechanism is actually dependent on the alcohol
concentration and also on the polarization time. At low glyc-
erol concentrations, the first reaction product is formate that is
further converted into CO2 giving rise to carbonate species.
Note that the due to CO2 is visible because of the local acidic
pH resulted in hydroxyl consumption and the carboxylic
group formation in the thin electrolytic film between the elec-
trode and the CaF2 window [44, 46, 47]. In these conditions
and after long polarization time, oxalate is also formed indi-
cating a change in the reaction mechanism. At higher glycerol
concentrations, only formate is formed independently of the
reaction time.
Conclusions
Carbon-supported nickel nanomaterials were synthesized
from impregnation method to serve as anode catalysts toward
the glycerol oxidation in alkaline medium. Parameters such as
scan rate, temperature, and concentration of the supporting
electrolyte and that of the electro-reactive molecule were var-
ied with the aim at investigating their electrochemical effect
on the glycerol conversion at the surface of the electrode cov-
ered by catalytic oxyhydroxide species (-NiOOH). In gener-
al, the oxidative transformation of glycerol was a limited mass
transport reaction process. Thus, the peak potential and the
peak current of the glycerol oxidation on the Ni/C electrodes
shifted with the scan rate and with the temperature variation,
which is characteristic of an irreversible diffusion-controlled
phenomenon. This reaction starts in the beginning of the trans-
formation of -Ni(OH)2 species to -NiOOH. The glycerol
453
oxidation on -NiOOH layer is strongly dependent of the
OH concentration. In addition, the kinetics and the reaction
mechanism of the glycerol oxidation are relatively different
depending on the glycerol concentration as shown by in situ
infrared reflectance spectroscopy and voltammetric studies.
Indeed, formate was the main product formed at higher glyc-
erol concentrations, while at lower glycerol concentrations,
carbonate and oxalate were the mainly produced species.
Acknowledgments This work was mainly conducted within the frame-
work of a collaborative program CAPES/COFECUB under grant n Ch
747-12. V.L. Oliveira also thanks the CAPES Foundation (5444110) and
FAPESP (2008/11601-7).
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