Catalysis Communications 12 (2011) 772775

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Catalysis Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c a t c o m

Short Communication

Effect of deposition sequences on electrocatalytic properties of PtPd/C catalysts for

formic acid electrooxidation
Ligang Feng a,c, Fengzhan Si a,c, Shikui Yao a,c, Weiwei Cai a,c, Wei Xing a,, Changpeng Liu b,
a
b
c

State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, 5625 Renmin Street, Changchun, 130022, PR China
Laboratory of Advanced Power Sources, Changchun Institute of Applied Chemistry, 5625 Renmin Street, Changchun, 130022, PR China
Graduate University of the Chinese Academy of Sciences, Beijing, 100049, PR China

a r t i c l e

i n f o

Article history:
Received 16 December 2010
Received in revised form 10 January 2011
Accepted 12 January 2011
Available online 21 January 2011
Keywords:
PtPd catalyst
Formic acid electrooxidation
Catalytic characteristics

a b s t r a c t
PtPd/C catalysts with different surface compositions (Pt + Pd, PtPd and PdPt) were synthesized with
different deposition sequences, and characterized by electrochemical experiments and XPS measurements.
The different catalytic characteristics for formic acid electrooxidation occurred on the three PtPd/C catalysts
were preliminarily discussed according to the oxidation pathway. Due to the synergistic effect between Pt and
Pd, especially for Pt + Pd, the catalytic stability for formic acid oxidation was greatly increased. The results are
helpful in preparing of PtPd catalyst and understanding the oxidation mechanism for formic acid oxidation.
2011 Elsevier B.V. All rights reserved.

1. Introduction

2. Experimental

The research on the electrocatalysts for formic acid electrooxidation

(FAEO) is crucial for the development of direct formic acid fuel cell. In
recent years, Pt based and Pd based catalysts have been extensively
developed for FAEO [14]. It is accepted that FAEO on Pt catalyst
proceeds through a dual path mechanism, involving the direct path
and indirect path. During the reaction, signicant amounts of CO build
up on the catalyst surface blocking the reaction active sites. However, on
Pd catalyst, formic acid is oxidized to CO2 via a direct path, which
prevents the CO build-up on the catalyst surface.
The combination of Pt and Pd, for the purpose of integrating the
merits of each metal, may be a good way to increase the catalytic
activity or stability for FAEO. Several preliminary works about the
PtPd catalysts have been reported such as the effect of preparation
methods, the bulk composition or the surface modication with single
crystal Pt or Pd [2,59]. Because of the different mechanisms of Pt and
Pd for FAEO, it is inferred that different surface compositions of PtPd
catalysts should have different catalytic characteristics. In order to
understand the catalytic characteristics of PtPd catalysts, three PtPd/C
catalysts with different surface compositions were synthesized by
different deposition sequences and characterized by the electrochemical and physical measurements. The catalysts were evaluated for
FAEO and the catalytic behaviors were discussed by the oxidation
pathway. The results are helpful in preparing of PtPd catalyst for direct
formic acid fuel cell.

The PtPd/C catalysts with different surface compositions were

prepared by conventional impregnation reduction method [10,11]. In
brief, Pt+ Pd catalyst was synthesized by a co-impregnation reduction
method. PtPd and PdPt catalysts were synthesized by a stepwise
impregnation reduction method; namely, after the Pt (Pd) was
deposited on the carbon surface, the Pd (Pt) precursor was added and
reduced onto the as-prepared Pt (Pd)/C surface. The nominal weight
percentage of the metal (Pt and Pd) in the catalysts was 20% and the
atomic ratio of Pd and Pt was close to 1.
X-ray photoelectron spectroscopy (XPS) measurements were
carried out using a Kratos XSAM-800 spectrometer with Mg K
radiator. The electrochemical measurements were performed with an
EG&G Model 273A potentiostat/galvanostat and a three-compartment
electrochemical cell. A Pt plate and an Ag/AgCl electrode were used as
the counter electrode and reference electrode, respectively. All the
potentials were quoted against the Ag/AgCl electrode. The working
electrode was a thin layer of Naon impregnated catalyst on a glassy
carbon disk [11] and the catalysts loading was 0.38 mg cm2. All
electrochemical measurements were performed in 0.5 M H2SO4
solution with or without 0.5 M HCOOH deaerated by N2 at the room
temperature. The current density was normalized to the geometrical
surface area of the glassy carbon disk (0.07 cm2).

Corresponding authors. Tel.: +86 431 85262223; fax: +86 431 85685653.
E-mail addresses: xingwei@ciac.jl.cn (W. Xing), liuchp@ciac.jl.cn (C. Liu).
1566-7367/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2011.01.012

3. Results and discussion

There were no obvious differences in the PtPd/C catalysts in the
XRD patterns (not shown here) due to the similar atomic radii of Pt
and Pd and the very small lattice mismatch of Pt and Pd (0.7%) [8,12].

L. Feng et al. / Catalysis Communications 12 (2011) 772775

The nanoparticle sizes of the three catalysts calculated according to

the peak (220) by DebyeScherrer equation were mainly in the range
of 4.8 to 5.3 nm. Fig. 1 shows the XPS spectra of Pt 4f, Pd 3d and C 1s
for the three PtPd/C catalysts. The peaks of the C 1s for the three PtPd
catalysts were approximately 284.6 eV. The XPS spectra of Pt 4f and Pd
3d region were found to be composed of two pairs of doublets due to
the present state of the metallic and oxidized forms [13,14]. For Pt +
Pd catalyst, the peaks at 71.19 and 74.46 eV were ascribed to metallic
Pt, whereas the peaks at 72.11 and 75.41 eV were assigned to Pt (II)
species; the peaks at 335.57 and 340.83 eV were ascribed to metallic
Pd, whereas the peaks at 336.10 and 341.44 eV were assigned to Pd
(II) species. Similarly, for PtPd catalyst, the peaks at 70.70 and
74.05 eV were ascribed to metallic Pt, whereas the peaks at 71.36 and
74.68 eV were assigned to Pt (II) species; the peaks at 334.86 and
340.25 eV were ascribed to metallic Pd, whereas the peaks at 335.73
and 341.22 eV were assigned to Pd (II) species. For PdPt catalyst, the
peaks at 70.49 and 73.69 eV were ascribed to metallic Pt, whereas the
peaks at 71.02 and 74.70 eV were assigned to Pt (II) species; the peaks
at 333.55 and 340.33 eV were ascribed to metallic Pd, whereas the
peaks at 334.94 and 341.25 eV were assigned to Pd (II) species. It was
evident that the peaks of the binding energy for Pt + Pd catalyst were

773

shifted to higher binding energy values as compared to other two PtPd

catalysts, indicating a strong interaction between the Pt and Pd [14].
The Pt was mainly in the form of Pt metal, but the Pd was mainly in the
form of Pd oxide; it was due to that the Pd metal was easily oxidized to
the form of Pd oxide (Pd2+) at ambient conditions [14]. The atomic ratio
of Pt:Pd was 1:1.21, 1:1.87 and 1:0.34 for Pt+ Pd, PtPd and PdPt,
respectively. The atomic ratio of Pt:Pd in the catalysts surface for PtPd
and PdPt deviated from the nominal value of 1:1; it was due to the
different deposition sequences of Pt and Pd. For the PtPd catalyst, the
Pd was deposited onto the surface of as prepared Pt/C catalyst; For PdPt
catalyst, the Pt was deposited onto the surface of as prepared Pd/C
catalyst. This indicated that the PtPd catalyst or the PdPt catalyst
would have a Pd-rich or a Pt-rich surface, respectively. The surface
composition of the three PtPd/C catalysts obtained from XPS measurements was consistent with the expected PtPd surface composition.
The hydrogen adsorption/desorption curves of the Pt black, Pd
black and the PtPd catalysts are shown in Fig. 2. The potential value of
hydrogen desorption peak for Pt black, Pd black, Pt + Pd, PtPd and
PdPt catalysts was 0.148, 0.120, 0.165, 0.122 and 0.134 V,
respectively. The hydrogen adsorption strength for Pt + Pd catalyst
was obviously weakened. The reduction peak potential of the oxygen-

Fig. 1. XPS spectra for Pt 4f, Pd 3d and C 1s of PtPd/C catalysts.

774

L. Feng et al. / Catalysis Communications 12 (2011) 772775

Fig. 2. Hydrogen adsorption/desorption curves of Pt black, Pd black and PtPd/C catalysts

in 0.5 M H2SO4 with a scan rate of 50 mV s1.

containing species for Pt black and Pd black was 0.545 and 0.498 V,
respectively; it was 0.528 V for Pt + Pd catalyst, which was between
the potentials of 0.486 and 0.552 V for PtPd and PdPt catalysts. The
COad stripping voltammograms of the catalysts are shown in Fig. 3. For
Pt + Pd catalyst, the peak potential of COad oxidation was 0.65 V,
which was negatively shifted by about 70 mV and 50 mV as compared
to PtPd (0.72 V) and PdPt (0.70 V) catalysts, respectively. The
electrochemical surface area of Pt + Pd catalyst estimated from COad
stripping charge was the largest among the three catalysts. This was
an indication that there was a larger synergistic effect between Pt and
Pd, and it was helpful in weakening the CO adsorptive bond on the

Fig. 3. COad stripping voltammograms of PtPd/C catalysts in 0.5 M H2SO4 with a scan
rate of 20 mV s1.

active sites. From the above discussion, it was evident that the PtPd
catalysts with different surface compositions were successfully
synthesized.
Fig. 4 shows the cyclic voltammograms for FAEO on the PtPd/C
catalysts, Pt black and Pd black. For Pt black, there were three obvious
oxidation peaks in the positive direction, which were attributed to the
oxidation of hydrogen at 0.15 V, formic acid at 0.41 V and COintermediate at 0.70 V. In some research, it was proposed that the
FAEO in the potential region of 0.20.6 V was via a direct path [15]. In
fact, the current in that potential region was very small, and it may be
due to the poisoning effect of the accumulation of CO-intermediate
[16]. There was only one obvious peak on Pd black in the positive
direction which was assigned to FAEO through the direct path. It was
evident that Pd had much higher catalytic activity than Pt for FAEO.
The peak current was an indication of the catalytic activity of the
catalysts [3,4]. For PtPd catalyst, the peak current catalyzed by Pd
was 26.7 mA cm2 at 0.15 V; For PdPt catalyst, the peak current
catalyzed by Pt was 14.4 mA cm2 at 0.48 V. There were two formic
acid oxidation peaks for Pt + Pd catalyst with the current of
11.3 mA cm2 at 0.05 V catalyzed by Pd and 20.6 mA cm2 at 0.41 V
catalyzed by Pt, respectively. It was evident that the corresponding
peak potential for FAEO on Pt + Pd catalyst was negatively shifted as
compared with PtPd and PdPt catalysts. The catalytic characteristics
of PdPt catalyst were similar to the Pt black in the positive scan
direction. The oxidation region in the potential of 0.60.8 V was
assigned to the oxidation of the CO-intermediate; the potential region
of 0.20.6 V was attributed to FAEO catalyzed by Pt [17]. For Pd black
and PtPd catalyst, a similar oxidation peak appeared in 00.3 V due
to the FAEO through the direct pathway catalyzed by Pd. There was a
CO-oxidation peak on the PtPd catalyst indicating the existence of an
indirect oxidation path, but the current of FAEO catalyzed by Pt was
not obvious in the potential region of 0.30.6 V. The oxidation

Fig. 4. Cyclic voltammograms of PtPd/C catalysts, Pt black and Pd black in 0.5 M H2SO4 +
0.5 M formic acid with a scan rate of 20 mV s1.

L. Feng et al. / Catalysis Communications 12 (2011) 772775

775

relative stable current was obtained after about 300 s. According to

the above results, the FAEO at 0.4 V may mainly occur on the Pt
surface via indirect path, and at 0.2 V it may mainly occur on the Pd
surface through the direct path. Therefore, the introduction of Pt into
Pd is helpful for the stability of FAEO. For the Pt + Pd catalyst, though
the initial oxidation activity may reduce to some extent, the stability
has been largely improved.
4. Conclusions

Fig. 5. Chronoamperometric curves of PtPd/C catalysts in 0.5 M H2SO4 + 0.5 M formic

acid.

behaviors on Pt + Pd catalyst between 0.2 and 0.6 V were similar to

those of Pt black and PdPt catalyst; so it can be assigned to FAEO
catalyzed by Pt. The oxidation region of 0.1 to 0.1 V for the Pt + Pd
catalyst was much negatively shifted as compared to Pd black and Pt
Pd catalyst, which was due to the FAEO catalyzed by Pd in the direct
path. In the negative-scan direction, the catalytic characteristics of PtPd
and PdPt were very interesting. There was a spike in the curve for the
PdPt catalyst and the current was lower compared to other PtPd/C
catalysts. The current oscillation behavior was not frequently observed
for FAEO, so it was a surprise to observe the oscillation current on the Pt
Pd catalyst. During the initial negative scan, the noble metals Pt and Pd
in the catalyst should be in the state of metal oxide, and the metal oxides
were gradually reduced with decreasing the potentials. The PtPd
catalyst with different metal oxides or metal reduced states may possess
different catalytic activities for FAEO, thereby leading to the current
oscillation.
According to the contributions of the different compositions in the
catalyst to the catalytic activity, the potentials of 0.2 V and 0.4 V were
chosen to compare the catalytic stability catalyzed by Pd and Pt,
respectively. For PtPd catalyst, the current at 0.4 V was low, as was
the PdPt catalyst at 0.2 V; therefore, it was insignicant to evaluate
the catalytic activity at that potential. According to the similar
contributions to the catalytic activity, the potential of 0.2 V was
chosen to compare the catalytic stability catalyzed by Pd between Pt
Pd and Pt + Pd catalysts, and 0.4 V was chosen to compare the
catalytic stability catalyzed by Pt between the PdPt and Pt + Pd
catalysts. The corresponding chronoamperometric curves of the PtPd
catalysts are shown in Fig. 5. It was evident that the Pt + Pd catalyst
had much higher stable current than that of the PdPt catalyst at 0.4 V
and it was also more stable than that of the PtPd catalyst at 0.2 V. At
0.2 V, the contribution to current was mostly from Pd; the initial
current of FAEO was high, but it was not stable even after about
1000 s. At 0.4 V, the contribution to current was mostly from Pt; a

Three PtPd/C catalysts with different surface compositions were

successfully prepared and characterized by electrochemical experiments. Due to the large synergistic effect between Pt and Pd, the
oxidation of hydrogen, COad and formic acid became much easier on
the Pt + Pd catalyst. For the FAEO, especially in the negative scan
direction, the three PtPd/C catalysts had different catalytic characteristics. The combination of Pt and Pd would cause a decrease in the
initial catalytic activity, but the catalytic stability was largely
increased for FAEO.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (20703043, 20876153, 21073180, 20933004,
and 21011130027), Science & Technology Research Programs of Jilin
Province (20102204), High Technology Research Program (863
program, 2007AA05Z159 and 2007AA05Z143) of the Science and
Technology Ministry of China.
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