i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7

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Rapid fabrication of Cu/Pd nano/micro-particles

porous-structured catalyst using hydrogen bubbles
dynamic template and their enhanced catalytic
performance for formic acid electrooxidation

Reza Ojani*, Zeynab Abkar, Ehteram Hasheminejad, Jahan-Bakhsh Raoof

Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry,
University of Mazandaran, 3rd Kilometer of Air Force Road, 47416-95447 Babolsar, Iran

article info abstract

Article history: In this work, a self-supporting PdeCu bimetallic film with 3D porous structure was elec-
Received 21 December 2013 trodeposited at the surface of glassy carbon electrode (GCE) using a facile double-template
Received in revised form fabrication process, including hydrogen bubble templating method and galvanic replace-
5 March 2014 ment reaction, and its performance investigated as a catalyst for formic acid oxidation
Accepted 14 March 2014 (FAO). The structure of the Cu/Pd porous film was characterized by scanning electron
Available online 14 April 2014 microscopy (SEM) and energy dispersive spectroscopy (EDS). The electrocatalytic activity of
the as-prepared catalysts with high surface areas were evaluated in sulfuric acid solution
Keywords: containing 1 M formic acid using cyclic voltammetry (CV), linear sweep voltammetry (LSV),
Cu/Pd porous structures chronoamperometry and electrochemical impedance spectroscopy (EIS). The Cu/Pd porous
Hydrogen bubbles template structure exhibited significantly high current densities of formic acid oxidation compared
Galvanic replacement to the Cu/Pd particles film catalyst. The effects of galvanic replacement time and con-
Electro-oxidation centration of formic acid on the catalytic activity of as-prepared electrode for FAO were
Formic acid comparatively investigated.
Copyright ª 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

via a more direct pathway, bypassing the strongly bound CO

Introduction
Energy storage devices including fuel cell, Li-batteries etc.
have been developing especially today [1,2]. Among them,
direct formic acid fuel cells (DFAFCs) has been receiving much
attention as one of the most attractive energy sources [3]. Pd-
based electrocatalysts have recently attracted great attention
as promising anode catalyst for DFAFCs [4e9]. In contrast to
the commonly used Pt catalysts, Pd catalysts can catalyze FAO
intermediate [5,6]. Therefore, considerable efforts have
currently been directed to developing novel Pd catalysts.
Recent studies in the field of FAO have been focused on
increasing catalyst activity and durability through various
approaches. It has been demonstrated that formic acid
oxidation was more facile on Pd alloyed with a less expensive
metal M (M ¼ Fe, Co, Ni, and Cu etc.) [10e13] than on pure Pd
and the catalyst deactivation was much slower. For example;
Xu et al. [11,14] fabricated the PdeCu alloy particles with

* Corresponding author. Tel.: þ98 112 5342301; fax: þ98 112 5342302.
E-mail address: fer-o@umz.ac.ir (R. Ojani).
http://dx.doi.org/10.1016/j.ijhydene.2014.03.081
0360-3199/Copyright ª 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
Fig. 1 e Low (a, c) and high (b, d) magnification SEM images of Cu/Pd porous structure (a, b), Cu/Pd particles film (c, d).
superior electrocatalytic activity and stability for formic acid
oxidation. Han et al. [15] presented a facile one-pot synthesis
of highly monodisperse PdeCu bimetallic alloy nanoparticles
through the co-reduction of Pd and Cu precursors in non-
hydrolytic solutions by using tri-octylamine and oleic acid.
The alloying effect can be largely understood in the frame
work of the d-band theory [16]. The addition of the second
metal changes the electronic structure of Pd, decreases the Pd
d-band center and therefore weakens the adsorption of
inhibiting reaction intermediates. Another approach to
enhance ability of Pd catalysts involves the design of novel Pd
nano and microstructures with higher activity for formic acid
oxidation such as 3D porous materials [7,17].
In recent years, numerous efforts have been performed for
the preparation of porous materials due to their large surface
area and, as a result, higher catalytic activity. Because of their
large surface area, 3D porous materials have attracted
increasing interests in the fields of catalysis [18e20], fuel cell
[21], battery [22], sensor [23e25] and adsorbent [26]. One of the
most intensive topics concerning their synthesis is to tailor
the properties of the porous materials, including their
porosity, mechanical stability, and specific surface area.
7789
Nanoparticle-based, templating (substrate-based), dealloying
[12,27,28] and decoration techniques have been applied to
yield porous structure [29]. Among them, the most popular
approach to prepare such materials with controlled charac-
teristics is the template assisted method. Notably templating
can pre-define size and shape of porous structure [30] and the
H2 bubble technique presents a green and attractive template
for preparing 3D nano, micro-porous structure materials
[31e33], attributed to its low cost, ease of operation and facile
elimination of bubbles. In gas bubble dynamic template pro-
cess, the hydrogen bubbles arising from the electrochemical
reduction of Hþ in the deposition process functions as the
dynamic template for metal electrodeposition. Metal is elec-
trodeposited and grows within the interstitial spaces between
the hydrogen bubbles to form a porous film of metal on the
substrate. It overcomes troublesome procedures to remove
the traditional template, e.g. the drawback of using hard
templates lies in the requirement to apply strong chemical
treatment.
Based on above considerations, in this work, we report the
application of 3D porous Cu film with the flower-like structure
as a support for loading of Pd by galvanic replacement method
7790 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
to make highly porous PdeCu catalyst and investigation of its
catalytic ability for FAO. It is noticed that Cu as an assistant
component plays important roles in enhancing the catalytic
activity of Pd [34]. This catalyst exhibits a large active surface
area and a superior catalyzing activity. This double-template
synthesis process can be considered as an effective method
for Pd loading on less expensive metal such as Cu which leads
to design the efficient Pd-based catalysts with lower cost.
Experimental
Reagents and chemicals
CuSO4.5H2O, PdCl2, HCOOH, H2SO4, HClO4 and other chem-
icals were of analytical grade purchased from Fluka. Twice
distilled water was used to prepare reagent solutions. All re-
agents were of analytical grade and used without any further
purification.
Instrumentation
All electrochemical measurements were performed using
potentiostat & galvanostat (Ivium, 5612 AJ Eindhoven,
Netherlands). A conventional three-electrode system was
employed including a GCE (diameter, 2 mm) as the working
electrode, a platinum wire as the auxiliary electrode, and an
Ag/AgCl (saturated KCl (3 M)) electrode as the reference elec-
trode. All the experiments were carried out at room temper-
ature (20  1  C). The structure morphology and elemental
quantitative analysis of deposited catalysts were studied by
scanning electron microscope (model VEGA-Tescan, Razi
Metallurgical Research Center) equipped with an energy
dispersive spectrometer (EDS).
Working electrode preparation
The GCE was polished in alumina/water slurry, consecutively
ultrasonicated in absolute ethanol and distilled water for
5 min beforehand use. Electrodeposition of Cu at GCE was
carried out in 0.5 M H2SO4 with 0.05 M CuSO4 by potentiostatic
technique. The Cu/Pd porous structures were prepared using
template-engaged replacement reaction between the depos-
ited Cu and the aqueous PdCl2 solution. In a typical replace-
ment reaction, the deposited Cu was immersed in the
electrolyte solution containing 4.5  103 M PdCl2 and 0.1 M
HClO4 for 25 min at room temperature.
For comparison, Cu/Pd particles film was also fabricated in
the absence of hydrogen bubbles template according the same
procedures as described above with difference that electro-
deposition of copper was performed using 0.05 M CuSO4 so-
lution containing 0.1 M H2SO4 instead of 0.5 M H2SO4.
Results and discussion
Microscopic characteristics of the Cu/Pd catalysts
The electrocatalysts comprising Cu/Pd porous structures and
Cu/Pd particles film were characterized using SEM analysis to
observe the surface of modified electrodes. The micrograph of
the Cu/Pd porous structures and Cu/Pd particles film is shown
with different magnifications in Fig. 1. From Fig. 1(a), it is
observed that Cu/Pd nano/micro-porous film is distributed in
the form of the 3D interconnected structure with flower-like
morphology over a large area. The higher-magnification SEM
image (Fig. 1(b)) reveals that the flower-like structures are
composed of equiaxed nano/micro-particles. Fig. 1(c and d)
shows the SEM images of a typical Cu/Pd particles film with
non-porous nature. It can be seen that the electrode surface is
almost totally covered by microparticles with average size of
100e250 nm. AS shown in Fig. 1(d), each individual particle is
composed of several nanoparticles. Comparison Fig. 1(a and b)
with Fig. 1(c and d) confirms the significant effective role of
hydrogen bubbles template in the creation of 3D porous
structures.
To study the bulk composition of Cu/Pd 3D porous film in
more details, EDS analysis was performed (Fig. 2). The EDS
spectrum confirms the presence of Pd on Cu film demon-
strating Cu is simultaneously replaced with Pd. Elemental
analysis data given from EDS analysis after replacement of Cu
under-layer by Pd were listed in Table 1. It should be pointed
out that the energy peaks of Au appeared in the spectrum is
due to the gold-coating step of the electrode surface for SEM
imaging.
Voltammetric measurements (CVs and LSV)
Fig. 3 displays the 1st to 10th cyclic voltammograms of 0.5 M
H2SO4 solution at the surface of Cu porous structure modified
electrode. At the first scan, a big oxidation peak of Cu at 0.21 V
and a reduction peak of Cu oxides at 0.15 V were observed.
Both peaks decreased with the increase of scan cycle and
almost disappeared at the tenth scan due to the dissolution of
Cu. Herein, we estimated the Pd loading on the electrode using
the first Cu anodic stripping peak and also atomic ratio be-
tween Cu and Pd, obtained from EDS analysis, as follows: At
first, the number of moles for deposited Cu (molCu) was ob-
tained from Faradic law: molCu ¼ QCu/2F Where QCu is the
Fig. 2 e EDS spectra for the Cu/Pd porous structure catalyst
electrode.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
Table 1 e Parameters obtained from EDS analysis.
Element Line Wt%
C Ka 33.82
Cl Ka 1.77
Cu Ka 25.02
Pd La 27.60
Au Ma 11.80
Total 100.00
charge related to the first Cu stripping peak and F is the
Faraday constant (96,485.309 C mol1). Based on this, Cu
number of moles was found to be 1.036  107. Then,
considering ratio between atomic percentage of total Cu (Cu
replaced with Pd þ residual Cu) and Pd which is 18.25%/7.25%
the Pd number of moles at the electrode surface was obtained
to be 4.117  108 (according to the EDS). Finally, the amount
of Pd obtained from this consideration was calculated to be
0.14 mg cm2.
The CVs taken in 0.5 M H2SO4 for the glassy carbon elec-
trodes modified with Cu/Pd porous structure and Cu/Pd par-
ticles film (with same geometric area) are shown in Fig. 4. In
the acid medium, there are one pair of hydrogen desorption
peaks at 0.25 V and 0.13 V in positive scan and two
reduction peak at 0.17 and 0.23 V in negative scan for Cu/Pd
porous catalyst. Also, one pair of hydrogen desorption peaks
and a single hydrogen adsorption peak is observed for Cu/Pd
particles film. Additionally as can be seen, the peaks corre-
sponding to the formation of palladium oxide and its reduc-
tion appear at the potential ranges of 0.5e0.9 V and 0.2e0.3 V
respectively, for both catalysts. Obviously, the peaks on the
Cu/Pd porous structure are stronger than that on the Cu/Pd
particles film, which suggests the 3D porous catalyst has
larger surface area and better catalytic activity than itself non-
porous counterpart.
Among the several determining methods of electrochemical-
surface-area (ECSA) for Pd, the method of surface oxide reduc-
tion was chosen in this work because of its low deviation [35,36].
The charge density for monolayer of PdO was chosen to be
424 mC cm2. Therefore, the ECSA of the Pd-based catalysts was
measured by the following equation [37].
QR
ECSA ¼
QMR
Fig. 3 e The 1st and upper cyclic voltammograms of 0.5 M
H2SO4 solution at the Cu/GCE at a scan rate of 50 mV sL1.
7791
At%
78.69
1.39
11.00
7.25
1.67
100.00
Fig. 4 e CVs of Cu/Pd porous structure (a) and Cu/Pd
particles film modified electrodes (b) in 0.5 M H2SO4
solution at scan rate 50 mV sL1.
where QR is the columbic charge required for the PdO reduc-
tion (mC) which was obtained from Fig. 4 and QMR is the charge
for the reduction of the PdO monolayer (424 mC cm2).
Therefore, ECSA of Cu/Pd porous structure and Cu/Pd particles
film were calculated to be 1.22 cm2 and 0.46 cm2, respectively.
It is found that the Cu/Pd porous structure has a 2.65-fold
higher ECSA (1.22 cm2) compared to that of Cu/Pd particles
film (0.46 cm2) with the same geometrical area under the
identical conditions.
Fig. 5 presents the CVs results for the two catalysts, Cu/Pd
porous structure and Cu/Pd particles film, in a 1 M HCOOH
þ0.5 M H2SO4 solution. In the forward scan, formic acid
oxidation produced an anodic peak; while in the reverse scan
there was also an oxidation peak, which is attributed to formic
acid oxidation after the reduction of the oxidized Pd oxide and
the removal of the incompletely oxidized carbonaceous spe-
cies formed in the forward scan. The oxidation peak in the
forward scan is usually employed to evaluate the electro-
catalytic activity of the catalysts and the anodic scan allows
the formation and builds up of the poisonous intermediate.
Fig. 5 e CVs of Cu/Pd porous structure (a) and Cu/Pd
particles film modified electrodes (b) in 1 M HCOOH D 0.5 M
H2SO4 solution at scan rate 50 mV sL1.
7792 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
The Oxidation of formic acid mechanistically proceeds by a
dual pathway [38e40]. One is the direct way in which formic
acid is oxidized directly into CO2 through a dehydrogenation
reaction avoiding the formation of COads poisoning
intermediate:
HCOOH/CO2 þ 2Hþ þ 2e Dehydrogenation pathway (1)
The second way is the indirect way through a dehydration
reaction involving the formation of COads poisoning interme-
diate followed by oxidation of this intermediate into CO2:
HCOOH/COads /CO2 þ 2Hþ þ 2e Dehydration pathway
(2a)
As shown in curve 5a, there is a main current peak for Cu/
Pd porous catalyst between 0.0 and 0.3 V and one shoulder
near 0.45 V, similar to the observations of Chen and co-
workers on nanoneedle-Covered Pd Ag Nanotubes [41]. The
main peak between 0.0 and 0.3 V corresponds to FAO on active
surface sites that have not been poisoned by COads (direct
path), while the small shoulder peak near 0.45 V may be
attributed to the oxidation of both COads and formic acid as a
consequence of the recovery of surface active sites by COads
oxidative removal [42]. It is found that the accumulation of
COads on the Pd surface during FAO can originate in dehy-
dration of HCOOH molecules (indirect path) [43] or/and in
electrochemical reduction of CO2 that is formed through
dehydrogenation pathway (as a new path from formic acid to
COads). In the case of latter, several recent spectroscopic
studies of HCOOH oxidation on Pd showed new light on the
mechanism of HCOOH oxidation on Pd and its deactivation
[44,45]. However, based on different analysis, it was found that
the slowly accumulated COads is not formed by the HCOOH
dehydration but arises from the reduction of CO2 produced in
dehydrogenation path. Based on these reports, we suggest
that the partial of accumulated COads on the Cu/Pd porous
catalyst may originate from the reduction of CO2. Further-
more, COads can be produced through dehydration pathway of
FAO on the Cu/Pd porous catalyst. The further proofs to
confirm the occurrence of dehydration pathway on the pre-
sent catalyst are given at succeeding EIS measurements in
Section 3.4.
However, the main peak is much larger than that near
0.45 V, indicating that the FAO on Cu/Pd porous structure
catalyst is mainly through the direct pathway. In the case of
Cu/Pd particles film, cyclic voltammogram (curve 5b) also in-
cludes a main oxidation peak and a small one in the forward
scan. Investigation of two cyclic voltammograms (a,b) reveals
3-fold higher current density for the main peak and also
higher ratio between the current densities of the main peak
and the shoulder at the Cu/Pd porous structure in comparison
with Cu/Pd particles film. These results suggest stronger
electrocatalytic activity towards FAO and less progress of FAO
through the COads pathway on the surface of 3D porous
catalyst compared to non-porous counterpart.
Additionally, it should be mentioned that the electro-
catalytic activity of 3D porous catalyst modified electrode for
FAO in terms of specific activity (normalized to ECSA of Pd)
and mass activity (normalized to loading of Pd) was compared
with results obtained for the different catalysts in the
literature [46e48]. Although the nature and concentration of
testing solution have a significant effect on measured FAO and
consequently FAO specific activity and mass activity, Table 2
shows obtained results are better than the results presented
by other research groups. While the present method is very
simple and allows the easy and low cost preparation for an
effective electrode based on the cheap Cu under-layer.
Fig. 6 shows the CVs of 1 M HCOOH in 0.5 M H2SO4 solution
at the surface of glassy carbon electrodes modified with Cu
porous and Cu/Pd porous structure. Obviously, no oxidation
peak for FAO was observed at the surface of Cu/GCE, indi-
cating that Cu has no electrocatalytic activity for formic acid
oxidation and in fact, the incorporation of Pd to 3D Cu porous
structure results to the catalytic activity for FAO. However,
there is a noticeable point in the case of Cu effect which is
named as synergism effect. As illustrated in the introduction
part, binary or even ternary catalytic systems often show
improved catalytic activity, attributed either to synergism or
“third body” geometric effects [49]. The synergism effect can
be meant a modification of the electronic properties of the one
metal, M1, by the presence of another, M2, (having a strain
and/or ligandeelectronic interaction origin) [49]. In the same
direction, the theory that can help the better understanding of
this effect is the “d-band center theory”, εd. Based on this
theory, d-band center of Pd plays a governing role in deter-
mining the affinity of this metal toward a variety of adsorbates
such as CO [49]. Thus, we suggest that the presence of Cu
atoms in present catalyst can improve the catalytic activity of
Pd towards FAO via the appearance of synergism effect. In
other words, the addition of Cu may decrease the Pd d-band
center and therefore weaken the adsorption of inhibiting
species.
Optimization of the experimental variable for the
preparation of catalyst
To improve the performance of the Cu/Pd porous catalyst, the
effect of the experimental conditions on the response of modified
electrode was investigated in detail. As to the deposition poten-
tial, Fig. 7(A and B) presents the cyclic voltammograms of the Cu/
Pd porous catalysts fabricated under different potentials for Cu
deposition (0.5, 0.7, 0.9, 1.1, 1.3 V) in 0.5 M H2SO4 solution
in the absence and presence of 1 M HCOOH, respectively. As can
be seen, the highest current density for PdO reduction (Fig. 7(A))
Table 2 e Comparison of obtained results for FAO at Cu/
Pd 3D porous structure with different Pd catalysts
presented in literature.
Catalyst Specific activity Mass activity References
(mA cm2) (mA mg1)
Cu/Pd 3D porous 3.0 822 Present work
structurea
Pd (thin)/Cua 0.8 e [46]
Pd@Ni/Cb 0.5 50 [47]
Pd/CNTb e 600 [48]
Pd/C ETEKb e 650 [48]
Pd/Cb 0.3 5 [47]
a
Test solution: 0.5 M H2SO4 þ 1 M HCOOH.
b
Test solution: 0.5 M H2SO4 þ 0.5 M HCOOH.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
Fig. 6 e CVs of Cu/Pd porous structure catalyst (a) and Cu/
GCE (b) in 1 M HCOOH D 0.5 M H2SO4 solution at scan rate
50 mV sL1.
and FAO (Fig. 7(B)) is appeared at the potential of 0.9 V for Cu
deposition. The possible reason is that the hydrogen evolution is
not obvious when the applied potential is more positive than
0.9 V and consequently the Cu deposited film is not porous
Fig. 7 e (A) CVs of Cu/Pd porous structures modified
electrode in 0.5 M H2SO4 solution at scan rate 50 mV sL1 for
various deposition potentials, (B) and in 1 M
HCOOH D 0.5 M H2SO4 solution for various deposition
potentials (a) L1.3, (b) L1.1, (c) L0.5, (d) L0.7, (e) L0.9 V.
7793
sufficiently, and also the amount of deposited Cu at the surface of
GCE is less when the potential is more negative than 0.9 V as
more negative potential leads to more hydrogen bubbles. Cu
deposition time was another parameter that was optimized.
Fig. 8 exhibits the voltammetric responses of Cu/Pd 3D porous
films including Cu structure deposited at different times towards
1 M HCOOH. It is clear that the highest FAO peak current density
can be observed for deposition time of 100 s. The effect of
galvanic replacement time was also studied on the electro-
catalytic behavior of formic acid onto Cu/Pd porous catalyst.
Fig. 9 shows the linear sweep voltammograms of as-fabricated
electrodes with different times for galvanic replacement of Cu
under-layer by Pd toward FAO in a 1 M HCOOH solution. The
relation between the peak current density and galvanic
replacement time is also shown as the inset of Fig. 9. It is clearly
observed that the time of 25 min for galvanic replacement has
maximum current density for FAO compared to other times.
Therefore, 0.9 V for deposition potential of Cu, 100 s for depo-
sition time of Cu and 25 min for galvanic replacement of Cu with
Pd were selected as the optimal conditions for further work.
Effects of formic acid concentration
The effect of formic acid concentration on the electro-catalytic
behavior of formic acid oxidation was investigated (Fig. 10). The
inset of this Figure shows the dependence of the peak current
density obtained from forward CV scan upon addition of formic
acid from 0.050 M to 3.0 M. It is clearly observed that the anodic
peak current density increase with increasing of formic acid
concentration linearly and level off afterwards at concentra-
tions higher than 1.75 M. This effect may be attributed to the
saturation of Pd active sites. Also, it is mentionable that the
peak potential shifts towards more positive values with
increasing HCOOH concentration. A possible reason for this
observation is the occurrence of IR drop due to high oxidation
current at higher concentrations [50].
Effect of potential sweep rates
Fig. 11 displays the effect of the potential scan rate (y), from 5
to 1000 mV s1, on the voltammetric behavior of FAO at the
Fig. 8 e CVs of FAO on the Cu/Pd porous structure modified
electrode in 0.5 M H2SO4 solution at scan rate 50 mV sL1 for
various deposition times H2SO4 solution for various
deposition times (a) 110, (b) 120, (c) 80, (d) 90, (e) 100 s.
7794 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
Fig. 9 e LSVs of FAO on the Cu/Pd porous structures
modified electrode in 1 M HCOOH D 0.5 M H2SO4 solution
at scan rate 50 mV sL1 for various galvanic replacement
times (a) 10, (b) 35, (c) 15, (d) 20, (e) 30, (f) 25 min.
Cu/Pd porous catalyst. As can be seen in the inset of Fig. 11, the
plot of peak current density versus square root of scan rate
exhibits a dual linear region. Hence, we can rationally assume
that the electrocatalytic oxidation towards HCOOH on the Cu/
Pd porous structure modified electrode in acidic solution is
controlled by the diffusion process. However, the possible
explanation for the appearance of dual linear region and
decrease of plot slope at higher scan rates is as follows: at
higher potential scan rates, the reaction product accumulates
in the vicinity of the electrode surface due to the higher re-
action rate, and it will prevent the contact of HCOOH mole-
cules with the surface active sites. Additionally, since the rate
of carbon dioxide production increases with increasing of
potential scan rate, more electrolytes will be expelled from the
pores of the electrode, thus decreasing the available surface of
catalyst for electrochemical reaction. The oxidation peak
Fig. 10 e LSVs of FAO on the Cu/Pd porous structure
modified electrode at scan rate 50 mV sL1 for various
concentrations of HCOOH (a) 0.05, (b) 0.1, (c) 0.2, (d) 0.4, (e)
0.6, (f) 0.8, (g) 1, (h) 1.25, (i) 1.5, (j) 1.75, (k) 2, (l) 2.25, (m) 2.5,
(n) 2.75, (o) 3 M.
Fig. 11 e LSVs of Cu/Pd porous structure modified electrode
in 0.5 M HCOOH D 0.5 M H2SO4 solution at different scan
rates:(a) 5, (b) 10, (c) 30, (d) 50, (e) 100, (f) 200, (g) 300, (h) 400,
(i) 600, (j) 700, (k) 800, (l) 900, (m) 1000 mV sL1.
potential shifted to more positive potentials with increasing
scan rate, confirming the kinetic limitation in the electro-
chemical reaction.
Chronoamperometric measurements
The electrochemical stability of Cu/Pd porous structure for the
electrooxidation of formic acid was investigated by chro-
noamperometry experiments in 0.5 M HCOOH þ 0.5 M H2SO4
solution at 0.185 V as corresponding peak potential (according
to Fig. 5(a)), and the observed result was compared with that of
Cu/Pd particles film (obtained under corresponding peak po-
tential i.e. 0.04 V (according to Fig. 5(b)) as shown in Fig. 12. The
high current density observed in the initial stage for Cu/Pd
porous structure is due to a greater number of active sites
available for oxidation at the surface of 3D porous catalyst.
Curves a and b in Fig. 12 reveal that the current density for FAO
Fig. 12 e Time-current curves for Cu/Pd porous structure (a)
and Cu/Pd particles film (b) in 0.5 M HCOOH D 0.5 M H2SO4
solution at 0.185 and 0.04 V vs. AgCl j KCl 3 M, respectively.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 7 7 8 8 e7 7 9 7
Fig. 13 e (A) Nyquist diagrams of Cu/Pd porous structure
modified electrode in 0.5 M H2SO4 D 1 M HCOOH at the
various potentials (a) 0.0, (b) L100, (c) L150, (d) L200 mV,
(B) and at the potentials (a) 100, (b) 200, (c) 300, (d) 400, (e)
500 mV.
on the Cu/Pd porous structure after 500, 1000, 2000 and 3000 s is
0.8, 0.6, 0.35 and 0.15 mA cm2, respectively, which is w 37%,
28%, 16% and 7% of the initial value whereas, this current
density is 0.4, 0.25, 0.12 and 0.085 mA cm2, respectively for Cu/
Pd particles film i.e. w30%, 18%, 9% and 6% of the initial value.
So it can be concluded that Cu/Pd 3D porous structure is more
stable, efficient and poisoning tolerant electrocatalyst for the
electrooxidation reaction in acidic media.
Electrochemical impedance spectroscopy (EIS)
In this study, EIS was used to investigate the mechanism of
formic acid oxidation. The different impedance behaviors in
different potential regions reveal that the mechanism and
rate-determining-step (r.d.s) in formic acid electrooxidation
vary with potentials. This could be illustrated by the similar
electro-oxidation of methanol on the PtRu/C [51]. According to
Wu et al. [51], electrochemical oxidation of methanol on the
PtRu/C is indicated by the following simplified model
assuming that only adsorbed COads is present as an
intermediate:
CH3 OH/COads þ 4Hþ þ 4e
COads þ H2 O/CO2 þ 2Hþ þ 2e
If the dehydration reaction (2) is the rate-determining
step, the impedance kinetic analysis shows that Nyquist
7795
plots are located in the first quadrant. However, if the reac-
tion (3) becomes the r.d.s, the Nyquist plots at low fre-
quencies fall into the second quadrant. Similarly, electro-
oxidation of formic acid on Pd or Pt catalysts could be
simplified in two steps: one is adsorption of formic acid on
the active sites of the catalysts to form adsorbed COads and
another is the further oxidation of the adsorbed species to
form CO2. At low potentials adsorption of the formic acid on
the active sites of the surface and its oxidation to produce
COads might be r.d.s for the FAO which is appeared as the
positive real impedances at the Nyquist plot. Similar elec-
trochemical impedance characteristic on the Cu/Pd porous
structures observes in the potential range 200 to 0.00 mV
(Fig. 13(A)) and the diameter of the arcs increases with in-
crease of potential which may be ascribed to the formation
and increasing accumulation of COads intermediate species
on the electrode surface. With increase of FAO potential in
the range þ100 to þ500 mV, further oxidation of the absorbed
formic acid species (i.e. oxidative removal of COads) on the
surface of the electrocatalysts may be considered as the rate-
determining step. The development of negative real axes
with the decrease of the frequency in Fig. 13(B) can be
attributed to the slow rate of the oxidative removal of COads
and this step can consider as the rate-determining step.
Therefore, EIS profiles reveal that indirect pathway is a
probable path for FAO on the Cu/Pd porous structure modified
electrode, consistent with the voltammetric response (Fig. 5)
where a small anodic shoulder is observed.
Conclusion
A simple double-template process was employed to fabricate
a 3D porous Cu/Pd bimetallic catalyst. The porous catalyst
obtained from the suggested process was compared to the
non-porous counterpart. Higher ECSA of Cu/Pd porous struc-
ture indicates that the present preparation method can
effectively increase active sites at the electrode surface which
leads to sensitive response to formic acid oxidation in com-
parison with Cu/Pd particles film. The results demonstrate
that the Cu/Pd porous catalyst has good activity, poison
tolerance and stability toward FAO. In addition, this prepara-
tion strategy is simple, green, and applicable to large-scale
synthesis. This result is useful to prepare efficient, cost-
effective and stable catalysts to improve fuel cell power.
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