Carboneceramic supported bimetallic PteNi nanoparticles

as an electrocatalyst for oxidation of formic acid

Biuck Habibi*, Nasrin Delnavaz
Electroanalytical Chemistry Laboratory, Faculty of Sciences, Department of Chemistry, Azarbaijan University of Tarbiat Moallem,
Tabriz, Iran
a r t i c l e i n f o
Article history:
Received 4 March 2011
Received in revised form
6 May 2011
Accepted 8 May 2011
Available online 12 June 2011
Keywords:
Platinumenickel nanoparticles
Electrocatalyst
Electrooxidation
Formic acid
Carboneceramic
a b s t r a c t
The PteNi nanoparticles supported on carboneceramic electrode (CCE) are prepared by an
electrodeposited process. The obtained catalyst is characterized by scanning electron
microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction and cyclic voltam-
metry. The results show that the PteNi nanoparticles (Flower like), which are uniformly
dispersed on carboneceramic, are 20e50 nm in diameters. The PteNi/CCE catalyst, which
has excellent electrocatalytic activity for formic acid (FA) electrooxidation than a compar-
ative Pt/CCE catalyst, shows great potential as less expensive electrocatalyst for FA elec-
trooxidation. On the other hand, the PteNi/CCE catalyst has satisfactory stability and
reproducibility when stored in ambient conditions or continues cycling. These results
indicate that the system studied in the present work is the most promising system for use
in direct formic acid fuel cells.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
During the past 20 years, direct methanol fuel cells have been
widely studied and considered as possible power sources for
the portable electronic devices and electric vehicles. These
fuel cells offer a variety of benets such as high specic energy
and the ready availability and portability of methanol. On the
other hand, the problem of methanol crossover from the
anode to the cathode through membrane leads to low system
efciency. Methanol crossover [1e5], prevents utilization of
high concentration of methanol; the limits generally less than
2 M. As an attractive candidate to replace methanol, formic
acid (FA), a non-toxic, non-explosive and non-ammable
liquid at room temperature has considerable advantages
[6e15]. The feasibility of direct formic acid fuel cells (DFAFCs)
based on proton exchange membranes has been demon-
strated by Masel and co workers [6,16]. Hsing and co workers
[17] have also reported that the rate of fuel crossover can be
reduced by a factor of 5 and thus a higher performance can be
obtained when FA is used in place of methanol under the
same conditions.
One of the main problems in proton exchange membrane
fuel cells is the development of anodic materials with high
electroactivity towards the oxidation of FA and methanol. It
is well known that platinum (Pt) is an effective electro-
catalyst for these oxidations. However, Pt is also highly
sensitive to CO-poisoning: the catalyst surface is progres-
sively poisoned by the adsorbed CO (CO
ads
), which is formed
as a result of the stepwise dehydrogenation of these oxidants
in oxidation reaction [18,19]. Poisoning CO
ads
species can be
oxidatively removed from the Pt surface through a Lang-
muir-Hinshelwood-type surface reaction with neighboring
OH
ad
species electrosorbed from water at more positive
potentials [20]. Thus, alloying of Pt with oxophilic metals
* Corresponding author. Tel./fax: 98 412 4327541.
E-mail address: B.Habibi@azaruniv.edu (B. Habibi).
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ he
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.05.062
enables electrochemical dissociation of water on oxophilic
metal sites at more negative potentials compared to pure Pt
and, therefore, allows electrocatalytic oxidation of CO
ads
at
lower anodic over potentials [21]. In order to improve the
electrocatalytic performance of the Pt catalyst for FA elec-
trooxidation, the Pt-based bimetallic catalysts, such as
PteAu [22e24], PteRu [25e27], PteBi [28,29], PteIr [30], PtePb
[31,32], PteSb [33], PteOs [34], PtePd [10,35], PteFe [36], PteSn
[36,37], and PteAg [38] have been investigated. However, to
the best of our knowledge, PteNi bimetallic catalyst for FA
electrooxidation has not been reported yet.
In this work, we have prepared CC supported PteNi
nanoparticles by a two-step procedure: (I) the CC substrate
was produced by using sol-gel technique and (II) PteNi
nanoparticles were precipitated electrochemically on the
surface of CC substrate and the resulting catalyst was
referred as PteNi/CCE. After surface, structural, and elec-
trochemical characterizations of the PteNi/CCE, the electro-
catalytic activity of PteNi/CCE towards the FA oxidation in
0.1 M H
2
SO
4
solution was evaluated by cyclic voltammo-
metric and chronoamperometric measurements and the
obtained results were compared with those obtained on the
smooth platinum and platinum nanoparticles CC electrodes.
It was found that PteNi/CCE was catalytically more active
than smooth platinum and platinum nanoparticles sup-
ported CC electrodes and had satisfactory stability and
reproducibility when stored in ambient conditions or
continues cycling.
2. Experimental
2.1. Chemicals
Methyltrimethoxysilane (MTMOS), formic acid, methanol,
H
2
PtCl
6
.5H
2
O, NiCl
2
, HCl, H
2
SO
4
and graphite powder of high
purity were obtained from Merck or Fluka. All solutions were
prepared with double distilled water.
2.2. Procedure of PteNi/CC preparation
Step I:
The sol-gel processing method was used for fabricating CC
substrate according to the following procedure: The amount
of 0.9 ml MTMOS was mixed with 0.6 ml methanol. After
addition of 0.6 ml HCl 0.1 M as catalyst, the mixture was
magnetically stirred (for about 15 min) until it produced a clear
and homogeneous solution. Then, 0.3 g graphite powder was
added and the mixture was shaken for another 5 min.
Subsequently, the homogenized mixture was rmly packed
into a Teon tube (with 3 mm inner diameter and 10 mm
length) and dried for at least 24 h at room temperature. A
copper wire was inserted through the other end to set up
electric contact. The electrode surface was polished with
emery paper grade 1500 and rinsed with water.
Step II:
Electrochemical deposition is an efcient method for the prep-
aration of metal particles. It is widely used with different strat-
egies/methodologies. Among these, potential step deposition
provides a tool to ne-tune the amount of the metal deposited,
the number of metallic sites and their size. The PteNi alloy
nanoparticles on CCE was electrodeposited (Potentiostatically)
froman aqueous solution of 0.1 MNa
2
SO
4
(pH3.8) comprising
different concentrations of H
2
PtCl
6
.5H
2
O and NiCl
2
(total
concentration of two salts equal to 1 mM) at 25

C. Before
deposition, the CCE was polished and subjected to electrode-
positionat a xedpotential of 0.4 Vversus a saturatedcalomel
electrode (SCE) for a certain time. The charge resulting fromthe
complete reduction of the precursor salts at the given time is
1384 mCcm
2
. This value corresponds to anequivalent amount
of platinum of 700 mg cm
2
when platinum is considered as the
only metal deposited [39]. After electrodeposition, the obtained
electrode was washed thoroughly with double distilled water
and dried before further investigation.
2.3. Instrumentation
The electrochemical experiments were carried out using an
AUTOLABPGSTAT-30(potentiostat/galvanostat) equippedwith
aUSBelectrochemical interfaceandadrivenGEPSsoftwarewas
used for electrochemical experiments. A conventional three
electrode cell was used at roomtemperature. The smooth(Pt or
CCE) or the modied electrode (Pt/CCE or PteNi/CCE) (3 mm
diameter) was used as a working electrode. An SCE and a plat-
inum wire were used as the reference and auxiliary electrodes,
respectively. JULABO thermostat was used to control cell
temperature at 25

C. Scanning Electron Microscopy (SEM) and
Energy-DispersiveX-rayspectroscopy(EDX) wereperformedon
a LEO 440i Oxford instrument. X-ray Diffraction (XRD) of the
PteNi nanoparticles was studied using a Brucker AXF (D8
Advance) X-ray power diffractometer with a Cu K
a
radiation
source (l 0.154056 nm) generated at 40 kV and 35 mA.
3. Results and discussion
3.1. Electrochemical characteristics of PteNi/CCE
To understand the electrochemical activity of the PteNi/CCE,
the cyclic voltammetric responses of the PteNi/CCE, Pt/CCE,
smooth Pt and CC electrodes were recorded at a scan rate of
50 mV s
1
. Fig. 1 shows the cyclic voltammograms (CVs) of the
PteNi/CCE, smooth Pt and CCE (inset A, curve 1 and 2,
respectively) and Pt/CCE (inset B) in 0.1 M H
2
SO
4
solution.
Although the typical Pt-peaks for the hydrogen under-
potential deposition (H
upd
), the oxidation of hydrogen (H
oh
),
formation of platinum oxide (PtO
for
), and its reduction (PtO
red
)
are present on the PteNi/CCE, they become ill-shaped
compared to the smooth Pt (inset A, curve 1) and even to the
unalloyed Pt modied CCE (Pt/CCE) (inset B) [40]. On the other
hand, compared with the Pt/CCE, both peaks for hydrogen
adsorption and desorption of PteNi/CCE decrease. In fact the
decrease of hydrogen peak was linear with the increase of
amount of Ni in the PteNi/CCE. So the contribution of the Ni
atoms (q
Ni
) deposited together with Pt atoms on the CCE
surface was calculated by the following equation [41]:
q
Ni
Q
bH
Q
aH
=Q
bH
(1)
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9582
Q
aH
is the electric charge of PteNi/CCE evaluated from the
cyclic voltammogram in the hydrogen region charge between
0.30 and 0.10 V in Fig. 1. Q
bH
is the electric charge measured
from Pt/CCE in the same region on the CV prole (Fig. 1, inset
B). In calculating the adsorptioncharge, i.e. the integrated area
under the peaks, we assume that the double layer capacitance
is constant across the entire potential range. Under the
deposition conditions [PteNi (70:30)], a stable Ni contribution
(0.31) can be easily got.
The actual active surface area of the PteNi/CCE is equiva-
lent to the number of Pt sites available for hydrogen adsorp-
tion/desorption. The PteNi/CCE produced Q
aH
of 1.07 mC.
Accordingly, the actual active surface area (A
r
) can be obtained
from charge for hydrogen adsorption as: A
r
Q
aH
/Q
0
(Q
0
has
been commonly taken as 210 mC/real cm
2
) 5.10 cm
2
.
The hydrogen adsorption charge of polycrystalline Pt was
calculated at 0.021 mC. These results show that the actual
active surface area of the PteNi/CCE is about 51 times larger
than that of polycrystalline Pt.
Curve 2 in inset A of Fig. 1 shows the CV of bare CC
substrate in 0.1 M H
2
SO
4
solution. No adsorption/desorption
peaks of hydrogen appeared at the bare CCE.
3.2. Non-electrochemical characteristics of PteNi/CCE
In order to surface characterization of the PteNi/CCE cata-
lyst, the micrograph of CCE and PteNi/CCE has been inves-
tigated by SEM and the corresponding results were shown in
Fig. 2. Fig. 2A shows the structure of the bare CCE surface
immediately after polishing with emery paper grade 1500. As
seen in this image the surface is dense, scaly and has a high
porosity. The average pore size of CC substrate is about
0.2 mm. Fig. 2B shows the SEM micrograph of the CCE surface
after PteNi deposition. As seen, the owers like PteNi
nanoparticles were obtained. The PteNi nanoparticles have
the size of 20e50 nm. High magnication shows (Fig. 2C)
that, each ower like structures of PteNi in this image is not
the individual PteNi crystallites. They are clews consisting of
crystallite aggregates.
EDX measurement was used to analysis the surface
composition of the catalyst. The EDX spectra of PteNi/CCE is
shown in Fig. 3A and the calculated chemical composition of
the some catalysts are listed in Table 1. The bare CCE data
(Fig. 3B) is also shown for comparison. It is evident that Pt and
Ni are present on the CCE support, indicating that the H
2
PtCl
6
and NiCl
2
precursors can be co-reduced to their respective
metal phases by electro co-deposition method from an
aqueous solution of Na
2
SO
4
.
The XRD pattern of PteNi/CCE catalyst is shown in Fig. 4.
The peak at approx. 55

(006) corresponds to the supporting

material (carboneceramic). The main characteristic peaks at
41.5

(111), 46.8

(200), 68.3

(220) for Pt and at 42.6

(010), 43.7

(002), 44.8

(111), 51.0

(200), 60.1

(012), 83.8

(220) for Ni were

observed, indicating the face-centered cubic (fcc) arrange-
ments. The X-ray diffraction patterns for Pt/CCE [42] and Ni/
CCE [43] show the diffraction peaks at 40.21

, 47.12

and 68.24

correspond to the (111), (200) and (220) facets of Pt crystal and

at 42.60

, 43.60

, 44.76

, 46.41

, 52.00

, 60.15

and 77.71

correspond to the (010), (002), (111), (011), (200), (012) and (220)
facets of Ni crystal, respectively. As can be seen in Fig. 4, fcc Pt
and fcc Ni have distinctive diffractions and hence can be
differentiated. It was also obvious that the XRD pattern of
PteNi/CCE catalyst combined the crystal features of Pt and Ni,
indicating the coexistence of both of them [44].
Fig. 1 e CV of PteNi/CCE in 0.1 MH
2
SO
4
at a scan rate of 50 mVs
L1
. The insets are (A) CVs of smooth Pt (curve 1) and bare CCE
(curve 2) and (B) Pt/CCE in the same conditions.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9583
3.3. Electrocatalytic properties of PteNi/CCE toward the
oxidation of FA
Fig. 5 shows the CVs of the PteNi/CCE and smooth Pt (inset A)
in a 0.5 M FA 0.1 M H
2
SO
4
solution. During the forward scan
of the CV of smooth Pt, the rst anodic peak results from FA
oxidation, while the second peak at 1.06 V can be attributed
to CO oxidation and FA oxidation on sites that were previ-
ously blocked by CO
ads
[11,30,45]. This is because CO
ads
is
generated as an intermediate during the electrochemical
oxidation of FA. The CV of PteNi/CCE shows the usual
characteristics of smooth Pt except that both for forward and
reverse scan directions the oxidation currents of FA on the
PteNi/CCE are signicantly higher than on the smooth Pt. It
can be seen from CV of FA oxidation on the PteNi/CCE that
the reaction commences in the hydrogen region and
proceeds slowly in the positive direction, and then reaches
a plateau at ca. 0.28 V. At potentials with more than ca.
0.35 V, the reaction becomes accelerated and maximum rate
at ca. 0.80 V occurs. Another increase in current at potentials
more than ca. 0.95 V and a rapid increase 1.35 are assigned to
the reaction intermediates and poisonous adsorbed species
to CO
2
[46e48] and oxygen evolution reaction [49], respec-
tively. Upon reversing the potential sweep, a very steep
increase of the reaction rate at ca. 0.48 V develops and
a maximum current is observed at ca. 0.38 V. After that, the
current gradually decreases but the reaction rate is still
faster than in the forward scan. This large anodic peak in the
reverse scan is attributed to the removal of the incompletely
oxidized carbonaceous species formed in the forward
scan [32].
A closer examination of the onset potential regions in
Fig. 5 compared to the FA free electrolyte shows that the
magnitudes of the hydrogen adsorption/desorption peaks
were reduced and disappeared by the presence of FA (inset B
Fig. 5), implying that FA is adsorbed preferentially on the
electrode surface at those potentials [50e52]. It should be
noted that, for low concentration of FA (not shown), the
hydrogen adsorption/desorption peaks are still visible
Fig. 2 e SEM images of (A) CCE surface immediately after
polishing, (B) same electrode after PteNi nanoparticles
deposition (PteNi/CCE) and (C) PteNi nanoparticles with
high magnication.
Fig. 3 e EDX data for the PteNi nanoparticles modied CCE
(A) and bare CCE (B).
Table 1 e Surface composition of PteNi/CCE catalyst.
Element Atomic
content, %
Mass
content, %
Measurement
error, %
C 16.18 1.94 0.55
Si 27.79 6.68 0.65
Pt 38.66 63.06 1.50
Ni 17.37 28.32 0.35
Total 100 100 e
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9584
showing that FA does not prevent completely the hydrogen
adsorption.
It has been widely accepted in the literature that FA in the
forward scan is oxidized to CO
2
via a dual path mechanism
on Pt [53e55], which involves a reactive intermediate
(dehydrogenation pathway) and CO
ads
as a poisoning species
(dehydration pathway) (Scheme 1). In one pathway, direct
oxidation of FA is said to occur (dehydrogenation pathway)
whereas in the other pathway, FA is oxidized to CO
(dehydration pathway), which in turns must be removed by
activating water. While the net reaction is the same in both
of the pathways, the water dissociation reaction is rather
difcult. The OH
ads
formed by the dissociation of water
molecules on Pt surface [56] aids in removing the adsorbed
surface poison CO
ads
by oxidizing it. But indeed this process
is very intricate, as a higher potential is required for water
activation (>0.5 V) on Pt surfaces. Consequently, the elec-
trode surface will be blocked by large amounts of CO
ads
species thereby hindering further adsorption of other FA
molecules on the electrode surface. This drawback will make
only a few number of FA molecules to be oxidized as the
electrode poison CO
ads
remains on the electrode surface for
a long time occupying active catalyst sites thereby reducing
the overall activity of FA oxidation. Hence, the rate of FA
oxidation primarily depends on the amount of CO
ads
removed from the electrode surface [57].
In the backward scan, a small reduction current peak
appears due to the reduction of Pt oxide to Pt.
PtO2H

/Pt H
2
O (2)
The backward oxidation peak has been attributed to the addi-
tional oxidation of the adsorbed carbonaceous species to CO
2
:
PtCO
ads
H
2
O/Pt CO
2
2H

2e

(3)
In comparison with Pt nanoparticles modied CCE [40];
PteNi nanoparticles modied CCE showed an enhanced
electrocatalytic activity towards the FA oxidation. The anodic
current density of FA oxidation on the PteNi nanoparticles in
forward scan is found increased to the 1.82 mA/cm
2
(actual
surface area A
r
), which is 0.31 mA/cm
2
(A
r
) for Pt/CCE in the
same condition [40]. While in the backward scan the anodic
current density is found 1.82 mA/cm
2
(A
r
), which is 0.64 mA/
cm
2
(A
r
) for Pt/CCE.
The effects of the alloying element (Ni) in the Pt-based
binary alloy on the electrooxidation reaction of FA can be
satisfactorily explained on the basis of (a) the bifunctional
mechanism, which should consider adsorption properties of
CO and OH surface species, (b) the electronic interaction
between the alloying element and Pt and (c) the increase in
electrochemical active area due to the leaching out effect of
the alloying element [58]. According to the bifunctional theory
Fig. 4 e XRD patterns of PteNi/CCE.
Fig. 5 e CV of 0.5 M FA on the PteNi/CCE in 0.1 M H
2
SO
4
at
a scan rate of 50 mV s
L1
. Insets A and B are the CV of 0.5 M
FA on the smooth Pt in the same conditions and the
expended hydrogen adsorption/desorption region (solid
line) in the absence and (dashed line) in the presence of FA,
respectively.
Scheme 1 e Schematic representation of FA oxidation on
the PteNi nanoparticles modied CCE.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9585
[59], an efcient catalyst favors CO adsorption on Pt and OH
ads
formation takes place on the second metal. Hence, the binary
combination yields the best overall activity for FA oxidation.
Therefore, CO adsorption mainly occurs on Pt, while OH
ads
species easily interact with Ni surface [60].
Ni H
2
O/NiOH
ads
H

(4)
NiOH
ads
PtCO
ads
/CO
2
Pt Ni H

(5)
Based on the above deduction, the ratio of the forward peak
current (I
pf
) to the backward peak current (I
pb
) reects the ratio
of the amount of FA oxidized to CO
2
to the amount of CO.
Hence the ratio of the I
pf
to the I
pb
, I
pf
/I
pb
, can be used to
describe the catalyst tolerance to carbonaceous species accu-
mulation. Basically, a higher I
pf
/I
pb
value represents a relatively
complete oxidation of FA, producing CO
2
, while; a low I
pf
/I
pb
ratio indicates poor oxidation of FA to CO
2
during the anodic
scan and excessive accumulation of carbonaceous residues on
the catalyst surface [61]. In other words, this ratio essentially
reects the fraction of the catalyst surface that is not poisoned
by CO
ads
and can be used to measure the catalyst tolerance to
CO-poisoning [50]. The ratio of I
pf
/I
pb
for PteNi/CCE in FA
oxidation is 1.0 which is more than 2 multiple higher than
those of Pt/CCE and Pt (0.49 and 0.39, respectively), which
indicated that more intermediate carbonaceous species were
oxidized to CO
2
in the forward scan on PteNi/CCE surface than
those on Pt/CCE and Pt surfaces. It is clear that, in PteNi
nanoparticles modied electrode, the presence of Ni provokes
the reaction to proceed through a direct pathway mechanism
or dehydrogenation mechanism wherein the reaction
proceeds without any poisonous intermediate. Therefore, an
enhanced oxidation rate towards the electrooxidation of FA is
observed due to the fact that Ni can increase the rate of FA via
a direct CO
2
pathway [62].
It should be noted that, in addition to the presence of
second metal (Ni), the nal potential in the cyclic voltam-
metric method can also affect the ratio of I
pf
/I
pb
in the elec-
trooxidation of FA on the PteNi/CCE (Fig. 6). With an increase
in the nal potential, the I
pf
remains constant while I
pb
decrease and consequently the ratio of I
pf
/I
pb
increase (Fig. 6,
insets A, B and C). In fact, increasing of the nal potential
accelerates the formation of Pt oxide. Acceleration of PtO
formation cases the acceleration of the dehydration pathway
and decreasing of CO
ads
and consequently decreasing of the
I
pb
. This phenomenon again shows that the ratio of I
pf
/I
pb
is
a sign of electrocatalytic and promoter activity of catalyst
toward the poisonous intermediate CO
ads
oxidation. In other
words by increasing the nal potential the conversion of
metal to metal oxides is accelerated and as a result, an
increase in reduction current peak of Pt oxide to Pt happens.
In case of potential of peaks, it can be seen (inset B) that the
potential of FA oxidation peak in the forward scan (E
pf
)
remains invariable, while the potential of oxidation peak in
backward scan (E
pb
) shifts positively and consequently
difference between E
pf
-E
pb
increases by increasing of nal
potential (inset C). In fact, the presence of high clean metal
nanoparticles surface improves poisonous intermediate
CO
ads
oxidation reaction thermodynamically and the lowers
potential peak of their oxidation in backward scan.
Fig. 6 e Effect of upper limit of potential scanning region on the electrooxidation of 0.5 M FA on the PteNi/CCE in 0.1 M
H
2
SO
4
. (1) L0.3e1.0 V, (2) L0.3e1.1 V, (3) L0.3e1.2 V, (4) L0.3e1.3 V, (5) L0.3e1.4 V, (6) L0.3e1.5 V, and (7) L0.3e1.6 V. Scan
rate 50 mV s
L1
. Insets are (A) Plot of anodic peak current in forward (I
pf
) (A) and in backward scan (I
pb
) (-), (B) Variation of
anodic peak potential in forward (A) and backward (-) and (C) plot of the ratio of I
pf
/I
pb
and difference between E
pf
eE
pb
as
a function nal potential.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9586
It is well known that the oxidation of FA like as other C
1
molecules on Pt alloys nanoparticles is strongly enhanced or
decreased by the change of heavy metals deposited (i.e., Ni). In
order to optimize the contents of electro co-deposited PteNi
nanoparticles on the CCE for FA oxidation, solutions with
various Pt/Ni (total concentration of two salts equal to 1 mM)
molar ratios were chosen. The metals loading were controlled
at 700 mg/cm
2
. The CV curve of FA oxidation on the eight
PteNi/CCE samples are drawn (not shown) and compared
with together. The peak current in the forward scan, the ratio
of I
pf
/I
pb
and the onset potential are three key parameters used
to evaluate electrocatalytic activity of different PteNi nano-
particles in the FA electrooxidation (Table 2). Because, in
addition to the peak current in the forward scan and ratio of
I
pf
/I
pb
it is generally recognized that the onset potential is an
indicator in electrocatalytic activity [61]. Table 2 shows that
the current of FA oxidation in forward scan are signicantly
enhanced after the introduction of second metal (i.e., Ni) and
all bimetallic PteNi catalysts exhibit high I
pf
/I
pb
values by at
least 12e104% higher than these in Pt/CCE catalyst. Such high
current ratio represents that most of the intermediate carbo-
naceous species can be oxidized to CO
2
in the forward scan on
PteNi catalysts [47,60]. Additionally, it should be noted that
the onset potential of FA oxidation depends on the content of
alloy (Table 2). On the other hand, the results indicate that the
PteNi nanoparticles electro co-deposited with the ratio of Pt/
Ni 70:30, exhibit the highest electrocatalytic activity, i.e. the
highest peak current in forward scan (9.4 mA), highest ratio of
I
pf
/I
pb
(1.0) and the lowest onset potential (0.15 V). Based on
the above results, it can be concluded that the PteNi/CCE
(70:30) catalyst has the greatest catalysis ability in the elec-
trochemically oxidationof FA. It is clear that all the PteNi alloy
catalysts present an activity enhancement for the FA oxida-
tion and the maximum electrocatalytic activity is found with
the Pt:Ni atomic composition (70:30), which is similar to that
obtained on the other Pt alloy [11,63e65]. In general, the
activity enhancement on Pt-based alloy catalysts could be
ascribed to the changes in structural parameters and the Pt-M
composition. In our work, it can be seen that the maximum
activity is found withthe Pt/Ni (70:30) atomic composition. i.e.,
When the content of Ni in the PteNi/CCE catalyst is increased
(0-30), in the ratio of Pt:Ni (70:30) the highest peak current in
forward scan, the highest ratio of I
pf
/I
pb
and lowest onset
potential are observed, suggesting that the increase in the
content of Ni in the PteNi/CCE catalyst changes the amount
and strength oxidation of FAmost probably via increase in the
nanoparticles surface area. However, the electrocatalytic
activity of the PteNi/CCE catalyst would be decreased when
the content of Ni in the PteNi/CCE catalysts is high (>40). This
may be attributed, on one hand, to the agglomeration of
formed particles to form clusters with lower surface area and,
on the other hand, to the low electrocatalytic activity on Ni for
the oxidation of FA. i.e., only when the atomic ratio of Pt and
Ni is suitable, such as PteNi/CCE (70:30) catalyst, its electro-
catalytic activity can be better than that of the other PteNi
mole ratio catalysts. So the activity enhancement in the
PteNi/CCE not only depends to addition of Ni to Pt/CCE cata-
lyst but also depends on the ratio of PteNi. Therefore the
combination of optimal PteNi nanoparticles with excellent
catalytic activity and CCE support with high electrochemical
accessible surface areas and stability can become a promising
electrocatalyst for FA oxidation in DFAFCs.
A further investigation was done to nd out the transport
characteristics of FA PteNi/CCE. The inuence of the scan rate
(y) on the electrooxidation of FA at the PteNi/CCE was inves-
tigated (Fig. 7). As shown in Fig. 7, the dependence of the
voltammetric prole with the scan rate is different in the
forward and backward scans. Whereas the backward scan is
almost insensitive to the scan rate (only small changes in the
maximum current obtained) [66], the currents recorded in the
forward scan increase as the scan rate increases. The anodic
peak currents are linearly proportional to y
1/2
(inset Fig. 7)
which suggests that the electrocatalytic oxidation of FA on
PteNi/CCE is a diffusion-controlled process [67,68].
Finally, in order to further assess the activity of PteNi/CCE,
the peak potential and peak current were determined as
a function of bulk concentration of FA. The obtained results
show that, the peak potential is shifted positively as the FA
concentration, but remained fairly constant, within a 50 mV
range over the whole change in concentration; meanwhile,
the anodic current at forward scanincreased linearly as the FA
concentration is increased.
3.4. Long-term stability of the PteNi/CCE
In practical view, long-term stability of the electrode is
important. The long-term stability of PteNi/CCE was exam-
ined in 0.1 M H
2
SO
4
solution containing 0.5 M FA (Fig. 8). It
can be observed that the anodic current remains constant
with an increase in the scan number at the initial stage and
then starts to decrease after 60 scans. The peak current of the
250th scan is about 90% than that of the rst scan. In general,
the loss of the catalytic activity after successive number of
scans may result from the consumption of FA during the CV
scan. It may also be due to poisoning and the structure
Table 2 e Comparison of electrochemical activities of the
different PteNi/CCE catalysts.
Catalyst
type
I
pf
(mA)
Onset
potential
(V vs. SCE)
I
pf
/I
pb
at
1st cycle
(dimensionless)
% (I
pf
/I
pb
)
PteNi/CCE
/
(I
pf
/I
pb
)
Pt/CCE
Pt (100) 1.8 0.0 0.49 e
PteNi/CCE
(90:10)
a
4.3 0.09 0.55 12
PteNi/CCE
(80:20)
7.2 0.12 0.82 67
PteNi/CCE
(70:30)
9.4 0.15 1.0 104
PteNi/CCE
(60:40)
7.4 0.11 0.94 91
PteNi/CCE
(50:50)
6.4 0.10 0.86 75
PteNi/CCE
(40:60)
5.0 0.09 0.80 63
PteNi/CCE
(30:70)
4.2 0.05 0.74 51
PteNi/CCE
(20:80)
3.1 0.01 0.70 43
a 0.9 10
3
M PtCl
6
.5H
2
O 0.1 10
3
M NiCl
2
.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9587
change of the metal nanoparticles as a result of the pertur-
bation of the potentials during the scanning in aqueous
solutions, especially in presence of the organic compound.
Another factor might be due to the diffusion process occur-
ring between the surface of the electrode and the bulk solu-
tion. With an increase in scan number, FA diffuses gradually
from the bulk solution to the surface of the electrode. After
the long-term CV experiments, the PteNi/CCE was stored in
water for a week; then FA oxidation was carried out again by
CV, and excellent catalytic activity towards FA oxidation was
still observed. This indicates that the PteNi/CCE composite
prepared in our experiment has good long-term stability and
storage properties. In order to further evaluate the stability of
the electrocatalytic activity of the PteNi/CCE towards FA,
chronoamperometric measurements were performed. Insets
(A and B) of Fig. 8 show the chronoamperometric curves of
0.5 MFA0.1 MH
2
SO
4
solution onthe PteNi/CCE and smooth
Pt electrode at 0.9 V for 4000s, respectively. It was found that
the currents observed from chronoamperograms were in
good agreement with the currents observed from cyclic vol-
tammetry. On the other hand, as can be seen the current on
the PteNi/CCE and smooth Pt electrode decreased with time
and reached at 4000s to 6.3 and 0.04 mA, respectively.
Compared to the smooth Pt electrode, the relative value of
the decrease for the PteNi/CCE is much lower. These results
show that the current represent less decay at the applied
constant potential on the PteNi/CCE for a long duration
(4000 s), indicating that PteNi/CCE exhibits a steady-state
electrolysis activity for FA oxidation. A further investigation
was done to nd out the effect of applied potential in chro-
noamperometric response of oxidation of FA at the PteNi/
CCE. Chronoamperometric data of the PteNi/CCE were
recorded by potential steps from 0 mV for 60 s to the various
potentials for 500 s. The current-time transient for the FA
oxidation at different anodic potentials shows that the
steady-state current at the ending time (t 500 s) increases
with an increase in applied potential. Phenomenologically,
the oxidation current increases slowly with time at 300 and
400 mV, while at higher potentials the current increases
sharply during short times and then decreases slowly at
longer times. This may be caused by the CO-poisoning effect
which results in deactivation of the catalyst surface and
blocks further oxidation of.
4. Conclusions
A bimetallic PteNi nanoelectrocatalyst with the PteNi atomic
ratio in surface layer 2.2:1 is synthesized by co-depositing on
highly prose carboneceramic from a solution of the corre-
sponding metals. FA electrooxidation at this catalyst was
studied. It was found that the catalytic activity of the
synthesized catalyst exceeds that of Pt nanoparticles (alone)
on CCE and smooth Pt electrode. The prepared catalyst
exhibits satisfactory stability and reproducibility when stored
Fig. 7 e Effect of scan rate on 0.5 M FA electrooxidation on
the PteNi/CCE in 0.1 M H
2
SO
4
. Scan rates are shown on
CVs. The inset shows the dependence of the forward
anodic peak currents on the square root of scan rates.
Fig. 8 e Plot of anodic peak current in forward scan (I
pf
) in
the electrooxidation of 0.5 M FA as a function of scan
number in cyclic voltammetric method at a scan rate of
50 mV s
L1
(Long-term stability of PteNi/CCE). Insets are
chronoamperometric curves in the same condition on the
PteNi/CCE (A) and smooth Pt electrode (B), respectively.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 9 5 8 1 e9 5 9 0 9588
in ambient conditions or continues cycling, which makes it
attractive as anode in DFAFCs and applications.
Acknowledgment
The authors gratefully acknowledge the research council of
Azarbaijan University of Tarbiat Moallemfor nancial support
of this research via grant/research fund number 401/475.
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