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Materials Chemistry
Cite this: DOI: 10.1039/c2jm16407h
www.rsc.org/materials COMMUNICATION
Pt–Au core/shell nanorods: preparation and applications as electrocatalysts
for fuel cells†
Chen-Wei Liu,a Yu-Chen Wei,a Chung-Chiun Liub and Kuan-Wen Wang*a
Received 6th December 2011, Accepted 3rd February 2012
Published on 13 February 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16407H

DOI: 10.1039/c2jm16407h
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Carbon-supported Pt–Au nanorods with a core/shell structure and In this study, we have successfully synthesized carbon-supported
excellent oxygen reduction (ORR) activities have been prepared. Pt–Au nanorods with core/shell structures by a facile wet chemical
The Pt shell nanorods exhibit high CO oxidation activity, while the reduction method.9 In order to provide a novel way for the fabrica-
PtAu shell nanorods benefits formic acid oxidation (FAO). The 1-D tion of high performance 1-D nanorods as electrocatalysts for fuel
morphology of the nanorods enhances the electrochemical activity of cells, the morphology and electrocatalytic activity correlation,
ORR, FAO and CO oxidation. including surface states/structures dependent ORR and FAO
performance of Pt–Au 1-D nanomaterials are also explored.
The 45 wt% Pt–Au/C nanorods with a Pt/Au ratio of 3 : 1 were
Nanostructured materials have been studied intensively due to their prepared via the formic acid reduction method. Two step reduction
versatile applications in the energy field.1 A large effort has been routes were used to synthesize Pt–Au/C nanorods with core/shell
devoted to develop highly efficient nanocatalysts for oxygen reduc- structures. In brief, aqueous solutions of H2PtCl6 (Alfa Aesar), and
tion reaction (ORR), formic acid oxidation (FAO), and alcohol HAuCl4 (Aldrich) with the stoichiometric ratio of 3 : 1 were blended
oxidation.2 Recently, carbon supported Pt nanowires exhibit superior and deposited separately at 340 K onto the commercial carbon black
performance for ORR due to their novel one-dimensional (1-D) (Vulcan XC-72R). The solution of H2PtCl6 and carbon were first
morphologies.3 The 1-D nanomaterials with higher aspect ratios, mixed and reduced by formic acid for 72 h, and then Au precursor was
fewer lattice boundaries, and fewer defect sites on the surface than the reduced by formic acid for another 48 h. The as-deposited catalysts
zero-dimensional (0-D) nanomaterials may display high ORR were subsequently dried at 330 K for 24 h, and stored as fresh PtAu
kinetics owing to their smooth crystal planes, balancing the interface shell nanorods. On the contrary, the Pt shell nanorods were prepared
between exposed Pt atoms and the oxygen adsorbates.2a,4 Further- by the initial reduction of Au precursor and following deposition of Pt.
more, 1-D electrocatalysts have shown improved durability for long- The exact metal loading and compositions of the Pt–Au nanorods
term applications compared to 0-D nanoparticles, which suffer from were examined by thermal gravimetric analysis (TGA), energy
irreversible oxidation of surface atoms on their defect sites.5 In dispersive spectroscopy (EDS) and inductively coupled plasma
addition, 1-D nanomaterials with structural anisotropy can enhance atomic emission spectrometer (ICP-AES) and are listed in Table S1
catalyst utilization and mass transport characteristics by path (ESI†). The exact Pt/Au atomic ratios of the Pt–Au nanorods are
directing effects, providing facile pathways for the electron transfer by approximately 3 : 1. The morphologies of the Pt–Au core/shell
reducing the number of nanoparticle interfaces.1a,6 nanorods were characterized by high resolution transmission electron
With respect to the catalysts for fuel cells, carbon supported Pt microscopy (HR-TEM) and ultra high resolution scanning electron
nanoparticles are the state-of-the-art electrocatalysts applied for the microscopy (UHR-SEM) as shown in Fig. 1 and S1.† Fig. S1a–
ORR at the cathode.7 However, Pt electrocatalysts are easy to b show the SEM images of the Pt shell and PtAu shell nanorods.†
dissolve and subsequently the Pt ions migrate to the solution in the The bare carbon spheres (Vulcan XC72R) with a diameter of 30–60
acid electrolyte during operation condition. Therefore, the addition of nm are covered randomly by Pt–Au nanorods. The TEM images
Au into the Pt catalysts is considered as a promising way to suppress shown in Fig. 1a–b display that the inherently anisotropic Pt shell
Pt dissolution during ORR and improve the long-term durability nanorods with lengths of 10–20 nm, are grown on the carbon spheres.
owing to the decrease in the oxophilicity and the change in Pt elec- The calculated interplanar lattice parameter of the Pt shell is
0.23
tronic properties.8 nm as shown in Fig. 1b, consistent with the (111) lattice plane of
bimetallic Pt–Au.10 On the other hand, for the PtAu shell nanorods,
the SEM and TEM images shown in Fig. S1b and 1c–d reveal that
a
Institute of Materials Science and Engineering, National Central the PtAu shell nanorods have a crystalline structure with an average
University, Taoyuan, 32001, Taiwan. E-mail: [email protected] length of 10–25 nm and a lattice parameter of 0.23 nm,† also in
b
Department of Chemical Engineering, Case Western Reserve University, agreement with the (111) lattice planes of bimetallic Pt–Au.10
Cleveland, 44106, USA. E-mail: [email protected] However, the core/shell components of the Pt shell and the PtAu shell
† Electronic supplementary information (ESI) available: Experimental
are not easily distinguished by TEM because Au and Pt exhibit
section, EDS, TGA, ICP-AES results, CV curves, XRD patterns and
Linescan results. See DOI: 10.1039/c2jm16407h similar imaging contrast and have the same crystal structure.11

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potential can easily be determined, providing semiquantitative

information on the composition of the outermost atomic layer of the
electrode materials.16 The typical CV features of bulk Pt–Au alloy
catalysts in sulfuric acid solution contain three regions: the pure
Pt/hydrogen adsorption/desorption region at E < 0.40 V, Pt oxide
formation/removal at E > 0.75 V and Au oxide formation/removal at
E > 1.15 V.17 The CVs for Pt–Au alloys catalysts tend to appear as
a linear combination of the CVs for both pure metals. When
compared to CV curves of Pt and Au catalysts, no oxidation peak of
Au is observed for the Pt59Au41 alloy catalysts, indicating that the
oxidation peak of Au can only be observed when Au > 41 at%.18 For
the typical voltammetric response of the Au surface, the oxide
stripping peak is located at 1.18 V.19 In terms of Pt, the oxide strip-
Published on 13 February 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16407H

ping peak is located at about 0.7 V.20 As shown in Fig. S3,† the
characteristic peak of Au located at 1.18 V for the PtAu shell
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nanorods is more significant than that for the Pt shell, indicating that
the surface Au of the former is richer than that of the latter, which
reflects the molecular level information for oxide products directly
obtained at the electrode–electrolyte interface. For Pt shell nanorods,
Fig. 1 HRTEM images of the Pt shell (a–b), and PtAu shell (c–d).
the main reduction peak located at 0.68 V implies that their surface is
completely composed of Pt species, while the surface of the PtAu shell
Although the synthetic process for the formation of 1-D nano- nanorods consists of Pt and Au species. This confirms that the
materials such as nanowires or nanorods always involves the use of preparation route significantly affects the core/shell structure of the
different kinds of surfactants or templates,12 in this study, the Pt Pt–Au nanorods. In addition to the electrochemical measurements
nuclei (or Au nuclei) are firstly formed in the solution by the reduc- shown in Fig. S3, the line scan results measured by HRTEM and
tion of precursors with HCOOH and then deposited onto the surface EDX are compared in Fig. S4 in the ESI.† On the basis of the Pt and
of C spheres without any surfactants or templates. The freshly Au atomic distributions, it can be observed that the Pt shell nanorod
produced nuclei can be considered as the sites for the further growth is rich in Pt on the shell. However, for the PtAu shell nanorod, the
of nanorods through the continuous absorption and reduction of Pt surface consists of both Pt and Au on the shell. The linescan results
and/or Au ions. Furthermore, the anisotropic growth, preferentially are consistent with the CV results depicted in Fig. S3.† Besides, the
in the [111] direction, is achieved by the quite slow reduction rate with electrochemical surface area (ECSA) value of the Pt/C, PtAu shell,
kinetically controlled growth and the lowest energy principle.9,13 and Pt shell catalyst determined by the integration of the charge
Based on this point, the Pt and Pt–Au shell nanorods along the associated with hydrogen adsorption/desorption region is 69, 29, and
closed-packed [111] direction can be obtained by this simple 35 m2 g1, respectively, as shown in Table S2.† The ECSA of Pt/C,
approach. which is consistent with the results reported in the literature,21 is much
Fig. S2 shows the XRD patterns of Pt–Au nanorods.† Based on higher than that of the PtAu shell and Pt shell nanorods.
the peak positions of face-centered cubic Pt (JCPDS #04-0802) and The ORR kinetics of the Pt shell and PtAu shell nanorods before
Au (JCPDS #04-0784) shown in the upper panels, the split peaks of and after 50 cycles (denoted as L) were performed using rotating disk
the Pt–Au nanorods can be indexed to the (111), (200), and (220) electrodes (RDE) and compared in Fig. 2. Table S1 summarizes the
reflections of the Pt-rich and Au-rich alloys. For the Pt shell and PtAu values of the current densities at E ¼ 0.8 V (I08) and the LSV results
shell nanorods, the patterns show intensive Au-rich and Pt-rich with a potential range of 0.3–1.0 V for Pt–Au nanorods and Pt/C
peaks, respectively, suggesting that the initial nucleation component, catalysts are compared in Fig. S5.† Notably, the ORR activities of
forming the large crystalline core, contributes substantially to the
pattern.14 Moreover, by fitting the (111) split peaks of nanorods, the
area ratios of the Au-based peak to the Pt-based peak is about 1 : 3,
implying that the starting materials form these two distinct solid
solutions with different sizes and compositions depending on the
preparation route. In other words, for Pt shell nanorods, once the Au
precursors are initially reduced on the carbon nanospheres, the
preferred orientation of the (111) plane for metallic Au is strongly
dominant and the large Au crystallites are rich in the inner core. On
the contrary, for the PtAu shell, Pt crystallites enrich the inner core
while the outer shell is covered by Pt and a small quantity of Au.
Based on the cyclic voltammetry (CV) and the linescan character-
izations, the formation of core/shell structures of Pt–Au are explored.
The core/shell structures of Pt–Au can be analyzed precisely by the
CV curves, which provide the information for assessing the relative Fig. 2 (a) The LSV recorded in 0.5 M H2SO4 saturated with O2 for Pt–
surface enrichment of Pt and Au.15 As displayed in Fig. S3,† the Au nanorods and Pt/C catalyst. (b) The long term tests of Pt–Au nano-
oxidation state of the surface atoms in each CV related to the applied rods collected after 50 cycles in 0.5 M H2SO4.

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the Pt–Au nanorods are both better than that of commercial Pt/C
0-D nanomaterials, even after 50 cycles. The promotional effect of the
Pt–Au nanorods may be attributed to the surface Pt enrichment and
the 1-D morphology,3 favorably enhancing the ORR activity. Based
on the long-term measurement observed in Fig. 2b, it can be seen that
both nanorods show the superior stability in 0.5 M H2SO4 solution.
Furthermore, for the PtAu shell nanorods, the Au peak located at
about 1.18 V becomes insignificant after 50 cycles, suggesting that the
surface atoms may be reconstructed under potential cycling condi-
tion. In addition, the Pt shell has better ORR activity before and after
50 cycles than the PtAu shell. Although Au clusters can have
a stabilizing effect on Pt, suppress Pt dissolution during applied
condition, and further enhance the durability of electrocatalysts.8c
Published on 13 February 2012 on http://pubs.rsc.org | doi:10.1039/C2JM16407H

The comparison in Fig. 2 suggests that the Au in the core part of the
Pt shell nanorods may show a better promotional effect on the ORR
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Fig. 4 (a) The CO-stripping in 0.5 M H2SO4 and (b) the forward scans in
performance than the surface Au in the PtAu shell nanorods. The the CVs for FAO in 2.0 M HCOOH and 0.5 M H2SO4 of Pt–Au
kinetic current density (Ik) determined by the Levich–Koutecky nanorods.
equation and the mass activity (MA) obtained by the normalization
of kinetic current to the weight of Pt of various catalysts are
compared in Table S2.† The Ik and MA of the Pt shell catalysts is 2.8 a deterioration of the CO oxidation than Pt/C. This can be explained
and 3.6 times higher than that of Pt/C, respectively. by the density functional theory (DFT) theory that a strong
On the other hand, the potential cycling experiments of accelerated adsorption of CO on the surface Pt sites owing to the presence of
durability test (ADT) were used to characterize the electrochemical surface Au may cause the deterioration of the electroactivity.22 On the
stability and performance of the Pt–Au nanorods and Pt/C cata- contrary, in terms of FAO activity shown in Fig. 4b, the PtAu shell
lysts.21 The ADT results depicted in Fig. 3a also show that the ORR nanorods, with surface Au enrichment, have superior FAO perfor-
activity of the Pt shell and PtAu shell nanorods at 0.85 V is both mance compared to Pt shell nanorods and commercial Pt/C. The
better than that of the Pt/C, which is consistent with the multiple CV existence of Au species on their surface can significantly enhance the
results. The ORR activity of the Pt shell is 1.3 and 2.6 times higher FAO electrocatalytic activity, consistent with the results that PtAu/C
than that of the PtAu shell and Pt/C after 1200 potential cycles. nanoparticles with surface enrichment of Au have a positive effect on
Meanwhile, a huge loss of ECSA for the Pt/C catalyst is observed as FAO compared to Pt/C and PtRu/C catalyst. Besides, a lower onset
shown in Fig. 3b. On the contrary, the relatively small loss of ECSA potential and large current density can be obtained for PtAu/C as the
found for the Pt shell indicates that it is more electrochemically stable proportion of Au increases.23
than the Pt/C. The normalized ECSA of the Pt shell and PtAu shell is In this communication, a facile wet chemical reduction method has
2.8 and 2.1 times higher than that of Pt/C after 1200 potential scans, been proved to successfully prepare the carbon-supported Pt–Au
respectively. nanorods with core/shell structures and excellent electrochemical
Besides ORR performance, the CO-stripping results are examined performance. The ORR activities and long-term durability of Pt–Au
in 0.5 M H2SO4 solution and compared in Fig. 4a. The Pt shell nanorods are both better than that of commercial Pt/C nanoparticles.
nanorods exhibit the best onset potential compared with the others, Besides, for Pt shell nanorods, the surface is completely composed of
suggesting the surface Pt is favorable for oxidation of molecular CO Pt species, exhibiting high CO oxidation activity. On the other hand,
and thus enhances the kinetics of CO-stripping. However, for the the surface of the PtAu shell nanorods consists of Pt and Au species,
PtAu shell nanorods, the surface enrichment of Au may induce which specifically benefits FAO. The promotional effect of Pt–Au
nanorods may be attributed to the 1-D morphology, favorably
enhancing the electrochemical activity of ORR, FAO and CO
oxidation.
This work was supported by the National Science Council of
Taiwan under contract no. NSC-100-2221-E-008-051.

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J. Mater. Chem. This journal is ª The Royal Society of Chemistry 2012