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Electrochemical deposition of AuePt alloy particles with cauliower-like microstructures for electrocatalytic methanol oxidation
Weichun Ye a,b,*, Huanhuan Kou a,b, Qinze Liu c, Junfeng Yan c, Feng Zhou c, Chunming Wang a,b,*
a

Department of Chemistry, Lanzhou University, Tianshui nalu No.222, Lanzhou, Gansu 730000, China Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, China c State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
b

article info
Article history: Received 9 August 2011 Received in revised form 23 November 2011 Accepted 25 November 2011 Available online 20 December 2011 Keywords: Electrochemical deposition AuePt alloys Cauliower-like microstructures Methanol electro-oxidation Electronic effect

abstract
AuePt alloy particles with cauliower-like microstructures of varying Pt/Au ratios were electrodeposited on indium tin oxide (ITO) substrates by constant potential electrolysis at E 0.25 V. The results of X-ray diffraction and X-ray photoelectron spectroscopy conrm that the bimetallic alloys can be obtained for different Pt/Au ratios including 4/1, 1/1 and 1/4. The formation of alloyed cauliower-like microstructures may be the result of the fast formation of gold seeds as the core and subsequent simultaneous deposition of Au and Pt from cyclic voltammetric study. The effect of surface composition of AuePt alloy particles on electrocatalytic methanol oxidation were investigated in H2SO4 solution. The electrocatalytic abilities including electrochemical surface area, peak current density and the turnover number of methanol oxidation follow the order of Pt4Au1 > Pt > Pt1Au1. The results can be ascribed to that electronic effect may be prominent while bifunctional effect is insignicant for AuePt alloy systems because the electrocatalytic activity of Au is negligible in acidic media. Additionally, the Pt4Au1 electrode has superior kinetics of methanol electro-oxidation than monometallic Pt electrode by calculating the electron transfer coefcient (a). Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Methanol electro-oxidation, as a promising solution to future energy problems, has received considerable attention due to the possible applications in direct methanol fuel cells (DMFCs), which show high-energy conversion efciency, low pollutant emission, low operating temperature and the simplicity of handling liquid fuel [1e4]. Over the past

decades, platinum is considered as the most suitable catalyst for methanol oxidation reaction, but a major problem is the poisoning of platinum by CO-like species generated during the electro-catalytic process [5e8]. Therefore, how to keep its activity and durability is of paramount importance. GoldePlatinum catalysts have attracted considerable interest in recent years because of not only their promising catalytic performance, but also the lower price and greater availability

* Corresponding authors. Department of Chemistry, Lanzhou University, Tianshui nalu No.222, Lanzhou, Gansu 730000, China. Tel.: 86 931 8912589. E-mail addresses: yewch@lzu.edu.cn (W. Ye), wangcm@lzu.edu.cn (C. Wang). 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.11.132

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of gold than that of platinum. The employment of gold in bimetallic AuePt catalysts could therefore produce a welcome reduction in the cost of fuel cell installations [9e16]. Several methods has been applied to prepare AuePt catalysts, such as co-sputtering [9], crossed-beam pulsed laser deposition [10], microemulsion [11], chemical co-reduction method [12] and electrochemical deposition [13e16]. Amongst these well-developed methods, electrodeposition is a simple method with low cost and easier control. Furthermore, electrodeposition is also a powerful and convenient tool to create hierarchical micro/nanostructures. Hierarchical micro/nanostructures are one type of hyperbranched structures which are generally formed by hierarchical selfassembly of freshly generated precursors under nonequilibrium conditions. They can provide high surface areas, special shapes, and chemical functionality, allowing them promising candidates for the design and fabrication of new functional nanomaterials. For example, porous Pt nanoowers were obtained by one-step and template-free electrodeposition, and the as-prepared Pt nanoowers exhibited remarkably higher catalytic activity and stronger poisoningtolerance for methanol electro-oxidation, compared to conventional nanosized Pt catalysts [17]. Electrochemical deposition was used to prepare palladium nanostructures with a 3D feather-like dendritic morphology [18] or nanoplates [19], both of which exhibited high electrocatalysis activities. We have recently developed an electrodeposition route to fabricate hierarchical dendritic gold microstructures on an indium tin oxide (ITO) substrate without the use of any templates, which displayed multifunctional applications such as electrocatalysis, surface-enhanced Raman scattering, superhydrophobicity and (super)oleophobicity [20]. However, the preparation of bimetallic particles with hierarchical micro/nanostructures by electrodeposition has not been tried as much. In this study, AuePt alloys with cauliower-like microstructures were fabricated on a surface of indium tin oxide (ITO) substrate by constant potential electrolysis in 0.5 M H2SO4 containing chloroauric acid and chloroplatinic acid. The resulting bimetallic particles were characterized with scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was found that these bimetallic systems demonstrated alloy properties for different Pt/Au ratios including 4/1, 1/1 and 1/4. The electrocatalytic behaviors of AuePt alloyed particles for methanol oxidation were investigated in H2SO4 solutions; the results show a higher catalytic efciency for Pt4Au1 composition.

2.2.

Electrochemical deposition of AuePt alloys

Prior to deposition, the ITO glass was washed with acetone, ethanol and water in sequence by ultrasounds, and then dried in N2. AuePt alloys were electrodeposited onto the ITO surface under constant potential electrolysis at E 0.25 V vs. SCE for 1500 s. The plating bath was the solution of 0.5 M H2SO4 containing a totaling 10 mM solution of chloroplatinic acid and chloroauric acid, and the molar ratios of chloroplatinic acid and chloroauric acid was adjusted as 5/0, 4/1, 1/1, 1/4 and 0/5, respectively. Herein, the corresponding samples were named as Pt, Pt4Au1, Pt1Au1 Pt1Au4 and Au. The co-electrodeposition process of Au and Pt was analyzed with cyclic voltammetry (CV). In CV, the potential was scanned from 1.2 V to 0.2 V at a scan rate of 20 mV1.

2.3.

Electrochemical measurements

The electrochemical measurements were carried out with a 273A electrochemical device (EG&G Princeton Applied Research). The ITO electrode modied with AuePt alloys served as a working electrode with an area of 0.196 cm2. The counter electrode was a platinum wire and the reference was a saturated calomel electrode (SCE). The CV experiments were performed in 0.5 M H2SO4 with or without 1 M CH3OH. After voltammetry in 1 M CH3OH of 0.5 M H2SO4 was tested with the same electrodes, chronoamperometry curves for 1500 s were immediately recorded at 0.75 V.

2.4.

Characterization

The morphologies of the samples were observed by a eld emission scanning electron microscope (FE-SEM, JSM-6701F, JEOL Inc., Japan) equipped with Kevex sigma energy dispersion X-ray (EDX) analysis tool. EDX spectrum was acquired over a collection time of 100 s using an operation voltage of 10 kV. An X-ray diffraction analyzer (XRD, Rigaku D/max-2400, Cu K-Alpha radiation, l 0.1541 nm) was used to determine the crystalline structures of the deposits. Chemical composition information about the samples was obtained by X-ray photoelectron spectroscopy (XPS), the measurement was carried out on a multifunctional spectrometer (Thermon Scientic) using Al Ka radiation, and the binding energies were referenced to the C1s line at 284.8 eV from adventitious carbon.

3.

Results and discussion

3.1. Characterization of the AuePt alloyed cauliowerlike particles

2.
2.1.

Experimental
Chemicals

Chloroauric acid (HAuCl4$4H2O), chloroplatinic acid (H2PtCl6$6H2O), H2SO4 and methanol were all of analytical grade and used without further purication. The solutions were prepared with Milli-Q water (18 MU cm, Millipore).

AuePt bimetallic particles were electrodeposited on the ITO surfaces under a xed potential electrolysis of 0.25 V for 1500 s in 0.5 M H2SO4 containing a total 10 mM concentration of HAuCl4 and H2PtCl6 with different molar ratios. To determine whether the AuePt bimetallic particles are aggregated together or a formed alloy of the two metals, the detailed XRD characteristics were compared with those of Au, Pt, and AuePt bimetallic systems (Au4Pt1, Au1Pt1, Au1Pt4). As shown in

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Fig. 1 e XRD patterns (a) (111) diffraction peak positions (b) and lattice constant (c) of the samples.

Fig. 1A, each pattern exhibits four diffraction peaks, which are assigned to (111), (200), and (220) faces of the face-centered cubic (fcc) structure of metallic Au and/or Pt. The diffraction peaks of the bimetallic particles appreciate a good shift from mono-metallic Au to mono-metallic Pt as the Pt content increases, and a linear relationship was found between the peak position (2q of (111)) and mole fraction of Pt in the electrolyte (Fig. 1B). The XRD proles corresponding to AuePt bimetallic systems exhibit a single and fairly symmetric peak of (111) face, which are intermediate between (111) peaks of Au and Pt; moreover, the values of lattice constant (d ) for the AuePt bimetallic particles are in between those of monometallic Au (0.407 nm) and Pt (0.388 nm) and increase linearly with the increase of Pt mole fraction in the electrolyte (shown in Table 1 and Fig. 1c), in which the lattice constant was calculated by Vegards law [21]. These suggest an alloy feature in which Au and Pt atoms were tightly mixed [22]. Fig. 2 represents typical SEM images of the as-deposited bimetallic particles on ITO substrates. The SEM images of

the monometallic Au lm display large and dendrite-like structures (Fig. 2A). Contrarily, as shown in Fig. 2E, the lm of pure Pt consists of porous nanoower-like structures, which is consistent with the previous studies [17]. Parts of (B)(D) of Fig. 2 display the SEM images of Pt1Au4, Pt1Au1 and Pt4Au1 samples: all AuePt alloy particles are formed as cauliower-like particles with rough surface which present rather special. Each cauliower-like particle is the conglomeration of numerous grains, which goes through three steps during the growth process: (i) formation of nuclei, (ii) tiny particles aggregation on nuclei and (iii) growth of nucleus into crystal grains. To study the bulk composition of AuePt alloyed particles in more details, EDX analysis was performed. Fig. 2F shows the EDX spectrum of AuePt alloy particles. The peaks of Au Ma1 and Au La1 are located at about 2.2 and 9.7 keV, respectively. The peaks at 2.2 and 9.4 keV correspond to Pt Ma1 and Pt La1, respectively. Except for the strong peaks from the substrate such as Si and O elements, no other peaks were observed.

Table 1 e Parameters obtained from XRD and EDX data. Sample Peaks position (2q/deg) (111)
Au Pt1Au4 Pt1Au1 Pt4Au1 Pt 38.3 38.5 39.0 39.6 40.3

d (nm)

Ratio of Pt:Au in electrolyte

Atom ratio of Pt:Au from EDX data

(200)
44.5 44.7 45.2 45.9 46.8

(220)
64.8 65.1 65.7 67.3 68.3 0.407 0.405 0.400 0.394 0.388 0:5 1:4 1:1 4:1 5:0 0:1 1 : 6.05 1 : 1.32 1 : 0.39 1:0

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Fig. 2 e SEM images of the samples of Au (A), Pt1Au4 (B), Pt1Au1 (C), Pt4Au1 (D) and Pt (E). (F) and (G) represent EDX and XPS spectra of AuePt alloy, respectively. The insets of (A)e(E) show the corresponding images at 50,0003.

Similar results were obtained by XPS measurement (Fig. 2G), indicating that the surfaces of the deposited AuePt alloyed particles are clean. According to the EDX data, the atomic ratios of Au and Pt are listed in Table 1. It is found that the bulk content of Au is slightly higher than its content in the electrolyte for all AuePt metallic systems. Apparently, AuePt alloy particles with different Au/Pt ratios can be easily obtained by

adjusting the Pt:Au molar ratio in the electrolyte, which may lead to different catalytic activities. To further analyze the composition distribution in a particle, the surface compositions of bimetallic particles were measured by XPS. Fig. 3 shows typical XPS spectra of Pt4f and Au4f regions of Au, Pt, and AuePt bimetallic systems (Au4Pt1, Au1Pt1, Au1Pt4). The peaks at 71.10 and 74.41 eV can be

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Both Pt4f and Au4f bands occur for AuePt bimetallic systems, indicating the co-deposition of Au and Pt. From the XPS measurements, it can be observed that the Au4f binding energies shift to a lower peak value for AuePt bimetallic systems compared to the positions for monometallic Au surface. This is related to the perturbed electronic interaction between Pt and Au atomic orbit, i.e. the formation of AuePt alloy [23], which could be attributed to the charge of Pt tends to transferring to Au due to the higher electronegativity of Au (2.54) in relation to Pt (2.2) in the presence of Au [24]. On the basis of intensities of the XPS peaks, the atomic ratios of Pt: Au of AuePt alloys could be obtained, and the results are indicated in Table 2. Except the case of Pt1Au4 that is a little different from the corresponding EDX data, the atomic ratios of Pt:Au for other samples are identical with the EDX data.

3.2.

CV study of formation mechanism of AuePt alloys

In our case, the standard redox potentials for the relevant couples can be expressed as follows: AuCl4 3e4Au 4Cl PtCl6 4e4Pt 6Cl
2

E0 0:99V vs:NHE E0 0:74V vs:NHE

(1) (2)

Fig. 3 e XPS spectra of Pt4f and Au4f for the samples.

assigned to Pt4f corresponding to monometallic Pt particles, while two Au peaks assigned to the 4f7/2 and 4f5/2 energy level appear at 84.12 and 87.81 eV for the monometallic Au surface. The Pt4f peaks can be assigned to Pt0 and Pt2 (respectively), as shown in the Supplementary data. The relative intensities of the different samples for Pt0 and Pt2 are shown in Table 2. Pt0 is found to be the predominant species in the samples. For Au4f of the samples, intensity of Au4f7/2 and Au4f5/2 exhibits a theoretical ratio of 4: 3, indicating Au to be present only in metallic state in the alloy without any surface oxide.

Here, NHE represents the normal hydrogen electrode. Obviously, gold ions are reduced before platinum ions, which is conrmed by the CV results (Fig. 4). Even for the i t electrodeposition process, CV is still a powerful tool to analyze the electrodeposition behaviors [25]. The typical evolution of voltammograms, covering the potential span 1.2 to 0.2 V in which the co-electrodeposition behaviors of Au and Pt took place, is illustrated in Fig. 4C. In order to identify the redox peaks, we have measured the CV curves for the electrodeposition of Au and Pt (respectively) under the same conditions, which are displayed in Fig. 4A and B. It is clearly seen in Fig. 4C that the deposition potential of Au is much higher than that of Pt, implying that gold ions are reduced more easily than platinum ions, while only one stripping peak for Au and Pt is observed, as compared with Fig. 4A and B. Also, the deposition peak potentials of gold and platinum in the second scan shift positive than those in the rst scan. The rst scan contains a characteristic nucleation loop which arises from the greater overpotential required for nucleation onto the bare electrode compared to deposition of metal onto metal [26], and subsequent growth occurs predominantly at the remaining metal sites rather than onto the surface of bare

Table 2 e Quantitative XPS data of AuePt alloys. Sample

Au Pt1Au4 Pt1Au1 Pt4Au1 Pt

Bind energy (eV)

Au 4f7/2 84.12, Au 4f5/2 87.82 Au 4f7/2 83.80, Au 4f5/2 87.48 Pt 4f7/2 70.50, Pt 4f5/2 73.84 Au 4f7/2 83.74, Au 4f5/2 87.42 Pt 4f7/2 70.50, Pt 4f5/2 73.85 Au 4f7/2 83.77, Au 4f5/2 87.45 Pt 4f7/2 70.96, Pt 4f5/2 74.29 Pt 4f7/2 70.96, Pt 4f5/2 74.43

Relative intensity of Pt0 : Pt2

63 : 37 86 : 14 78 : 22 56 : 44

Atom ratio of Pt : Au
0:1 1 : 3.37 1 : 1.42 1 : 0.44 1:0

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Fig. 4 e Cyclic voltammograms for deposition of Au in 0.5 M H2SO4 containing 10 mM HAuCl4 (A), Pt on 0.5 M H2SO4 containing 10 mM H2PtCl6 (B), and co-deposition of Au and Pt in 0.5 M H2SO4 containing 5 mM HAuCl4 and 5 mM H2PtCl6 (C). Potential was scanned with the rst cycle (dash line) and the second cycle (solid line) at 20 mV sL1.

ITO. This suggests that the growth is favored around the seeds once the metallic seeds have been formed. Although the detailed formation mechanism of AuePt alloyed cauliower-like microstructures is not clear, the formation of hierarchical microstructures may be the result of the fast reduction rate of metal ions and the corresponding fast nucleation and growth of hierarchical microstructures. Gu et al. reported the random sequential adsorption (RSA) process to produce gold cauliower-like structures by electrochemical deposition [27]. In the RSA process, the gold seeds were added sequentially on the substrate at random positions with the condition that the adsorbing particle could not overlap with a previously adsorbed particle. In this work, the deposition peak potentials for gold and platinum are much positive than the applied potential (0.25 V vs. SCE). So, gold and platinum can be deposited easily under this applied potential, due to strong driving force. The driving force for crystal nucleation and growth is completely correlated with applied potentials, which could control the morphologies of the deposits [18]. According to the CV results, gold is rstly deposited and platinum is sequently deposited on the as-deposited gold, and only one stripping peak rather than two peaks is observed. Therefore, it can be concluded that AuePt alloyed structures were formed based on the as-deposited Au as a modied core, and the formation of Au cores is crucial for the formation of AuePt cauliowerlike microstructures.

3.3. Effect of surface composition on methanol electrooxidation

The cyclic voltammetry in 0.5 M H2SO4 solution was employed to compare the electrochemically active surface area (SEl) of the samples. As expected, no features in the hydrogen adsorption and desorption region were found for the electrode with monometallic Au deposits (Fig. 5A), which is agreed with the reported results [28,29]. However, even as a small amount of Pt was introduced (Pt1Au4), weak peaks corresponding to the hydrogen adsorption and desorption could be observed. With increasing the amount of Pt content, the typical hydrogen adsorption/desorption peaks were obtained in the potential region of 0.26 to 0.1 V, as shown in Fig. 5B. It is worth noting that the incorporation of Au into Pt did not introduce obvious changes in the hydrogen adsorption/desorption regions compared with monometallic Pt. The potentials of the monolayer oxide (PtOx) reduction peak in the cathodic sweep for the electrodes of Pt1Au1, Pt4Au1 and Pt occurred at about 0.49 V. The currents in the adsorptionedesorption region for the electrocatlysts followed the order: Pt4Au1 > Pt > Pt1Au1. SEl of an electrocatalyst is one of the most important parameters to determine the catalytic activity for methanol oxidation. Herein, the SEl values of Pt, Pt4Au1, and Pt1Au1 are determined by the charge concerning H adsorption, QH, according to the following equation [30]:

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Fig. 5 e Cyclic voltammograms in 0.5 M H2SO4 solution in the absence (A, B, n [ 20 mV sL1) or presence (C, D, n [ 50 mV sL1) of 1 M CH3OH. (E) shows the chronoamperograms at 0.75 V for methanol electro-oxidation of 1 M CH3OH in 0.5 M H2SO4.

SEl

QH Q ref PtAu loading

(3)

The calculated values of SEl are listed in Table 3 for Pt1Au1, Pt4Au1 and Pt. It is clearly seen that small incorporation of Au into Pt has contributed to the increase of SEl (Pt4Au1) > SEl (Pt); when the ratio of Au in the AuePt alloy is high, the SEl decreases, SEl (Pt1Au1) < SEl (Pt). The electrocatalytic properties for methanol oxidation were measured in 0.5 M H2SO4 solution in the presence of 1 M CH3OH for each of the samples. It is found that the electrocatalytic activity follows the same order with the increase of SEl for the samples according to the data given in Table 3. In the potential range investigated, at the electrode modied with monometallic Au, no signicant voltammetric signal has been registered (Fig. 5C), whereas a noticeable anodic peak for the oxidation of methanol is observed even for a small amount of Pt incorporated into Au (Pt1Au4). In the reverse sweep, another anodic peak appears at 0.34 V, which is

attributed to the removal of surface adsorbed intermediate generated during the oxidation of methanol [31]. The results indicate that the Pt component plays a key role in methanol electro-oxidation. Obviously, the current densities of anodic peaks progressively increase with the increase of the amount of Pt in AuePt alloys, i.e., Pt4Au1 > Pt1Au1 > Pt1Au4, as shown in Fig. 5D and Table 3. Comparison of Pt-mass normalized methanol oxidation activities can help in understanding the Pt utilization of Pt alloy catalysts. Compared to the monometallic Pt electrode, a larger enhancement is observed at the Pt4Au1 electrode. Such an electrode has a considerably higher current density for methanol electro-oxidation. The results are attributed to the factors: Au in AuePt alloy aids in increasing the probability of inducing a major reaction pathway for methanol oxidation to avoid the formation of adsorbed CO [12]; the strong resistance to carbonaceous species accumulation is another important factor to evaluate the catalytic activity; the

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Table 3 e Comparison of electrochemical parameters. Electrode

Pt Pt4Au1 Pt1Au1

QH (mC cm2)
18.56 23.82 12.79

SEl (m2 g1)

88.38 113.43 60.91

Ep (V)
0.864 1.027 0.865

ip (mA cm2)
24.62 43.63 16.40

TON (s1)
0.53 0.89 0.024

electronic effect in AuePt nanoparticles is also important, where free electrons tend to ow from Pt to Au due to the difference in Fermi energy between these two metals [32]. In addition, the oxidation peak potential at Pt4Au1 shifted positively about 160 mV than that at Pt, which suggests that there may be some relation between the oxidation of methanol and Pt oxides [33]. Nonetheless, it is noticed that alloyed Pt with Au does not make the bifunctional effect because the electrocatalytic activity of Au is negligible (as seen in Fig. 5B). In contrast, Ru is the most promising component in Pt based binary catalysts for methanol oxidation by virtue of both the bifunctional effect and the electronic effect [34,35]. As the Au content in the AuePt alloy is large, its catalytic activity is still lower than that of pure Pt. As seen in Table 3, the current density of Pt1Au1 is only two-third fold as high as that of Pt. Consequently, keeping an enriched mass of Pt in AuePt alloy is necessary. Although some studies have been reported on an enhancement of the methanol oxidation reaction in the presence of Au [32,36], Au is not in the form of an alloy in AuePt bimetallic systems. The electrochemical stabilities of the AuePt alloy electrodes for methanol oxidation were investigated by

chronoamperometric technique at 0.75 V (Fig. 5E). It is noticeable that the current decays associated with the poisoning of the intermediate species followed in the same order with the CV measurements, Pt4Au1 > Pt > Pt1Au1. Pt4Au1 presents a current density of 1.11 mA cm2 after 1500 s whereas Pt and Pt1Au1 only have a current density of 0.66 and 0.03 mA cm2, respectively. To understand the differences of the electrocatalytic activity and stability for the samples, the turnover number (TON) was calculated for each catalyst. The TON is dened as the number of methanol molecules that react per catalyst surface site and this value directly reects the steady-state current density for methanol oxidation. As shown in Fig. 5E, the current density after 1500 s of the chronoamperometric experiment was considered to be the steadystate current density. From the steady-state current density, the TON is calculated using Eq. (4) [8].   molecules i 6:02 1023 TON nF 1:3 1015 site (4)

where i is the steady-state current density after1500 s process, n is the number of electrons produced by oxidation of 1 mol methanol (n 6), F is the Faraday constant, and the density of the topmost atoms of an ideal Pt(100) surface is about 1.3 1015 cm2. Table 3 summarizes the TONs for methanol oxidation on the three electrodes at 0.75 V. The Pt4Au1 catalyst appears to show the highest TON (0.89 s1), followed by Pt catalyst (0.53 s1) and then Pt1Au1 (0.024 s1), which demonstrates that the Pt4Au1 catalyst is available to catalyze the oxidation of more methanol for the same period with the same number of sites than the catalysts of Pt and Pt1Au1.

Fig. 6 e Voltammetric curves of methanol electro-oxidation at Pt (A) and Pt4Au1 (B) (scan rate 40, 50, 60, 80, 100, 120, and 150 mV sL1 from inner to outer). (C) ip and n1/2 plot and (D) Ep and log (n) plot.

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3.4. Comparison of the kinetics between Pt4Au1 and Pt electrodes

The investigation of the kinetic factor of methanol oxidation is another efcient approach to evaluate the catalytic activity of eletrocatalysts [37e39]. Herein, the relationships of peak current density (ip) and peak potential (Ep) for methanol oxidation with CV scan rate (n) have been studied, where the peak corresponds to the forward anodic peak. The cyclic voltammograms in 1 M CH3OH and 0.5 M H2SO4 with different scan rates at Pt4Au1 and Pt are shown in Fig. 6A and B, respectively. Fig. 6C shows the relationships between ip and square root of scan rate (n1/2) at Pt4Au1 and Pt electrodes, and there are both linear relationships for the two electrodes. It can be inferred that the oxidation of methanol at the two electrodes may be controlled by a diffusion process [40]. In addition, we found that the slope for Pt4Au1 electrode was larger than that for Pt electrode (2.24 vs. 2.09 mA). It is accepted that the peak current density is proportional with Ai [41]. Here, Ai is the active surface area of Pt catalysts per unit geometric of electrode. Therefore, it can be concluded from the slope values that Pt4Au1 electrode has larger catalytic activity for methanol oxidation than Pt electrode. The obtained relationships of Ep with log (n) corresponding to the electrodes of Pt4Au1 and Pt are shown in Fig. 6D. It is observed that the Ep values at Pt4Au1 and Pt electrodes rise linearly with log(n), and the linear slope for Pt4Au1 electrode is smaller than that for Pt electrode. In general, the linear relationship of between Ep and log(n) can be represented with the vEP 2:3RT=1 anF [42]. Here, n is given equation of K vlogn as 6, a stands for the electron transfer coefcient, characterizing the effect of electrochemical potential on the activation energy of an electrochemical reaction. Thus, the a values are calculated as 0.60 and 0.63 for Pt4Au1 and Pt electrodes, respectively. These indicate that methanol oxidation at Pt4Au1 and Pt electrodes are irreversible and the Pt4Au1 electrode has smaller activation energy and hence has enhanced kinetics of methanol electro-oxidation than monometallic Pt electrode.

promote the activity of methanol electro-oxidation mainly through electronic effect. In addition, Pt4Au1 has enhanced kinetics of methanol electro-oxidation than monometallic Pt. Because the prepared AuePt alloy particles have unique structural and catalytic properties, they will nd potential applications in the fabrication of novel micro/nanostructures and DMFCs.

Acknowledgment
This work is supported by the Natural Science Foundation of Gansu Province, China (No. 1107RJZA261) and the Fundamental Research Funds for the Central Universities (No. lzujbky-2011e25).

Appendix. Supplementary material

Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.ijhydene.2011.11.132.

references

4.

Conclusions

An electrochemical approach has been developed to prepare AuePt alloyed particles with cauliower-like microstructures on ITO substrates. In comparison, the lm of pure Au exhibits dendrite-like structures and the SEM images of pure Pt appear to be porous nanoower-like structures under the same electrodeposition conditions. The AuePt alloyed particles with different Pt/Au ratios can be modulated by controlling the molar ratios between metal precursors in the electrolyte. CV analysis demonstrates that the formation of the AuePt alloyed microstructures is attributed to the occurrence of gold cores due to fast reduction and subsequent simultaneous deposition of Au and Pt atoms around the cores. The electrocatalytic activities for methanol oxidation of the resulting AuePt alloyed electrodes were investigated in H2SO4 media. From the measurements of CV and chronoamperometry, the electrocatalytic efciency is in the order of Pt4Au1 > Pt > Pt1Au1. The Au atoms in AuePt alloys

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