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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
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
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
773
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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.
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