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Electrochimica Acta 52 (2007) 55995605

Electrocatalytic activity of carbon-supported PtAu nanoparticles for methanol electro-oxidation


In-Su Park, Kug-Seung Lee, Dae-Sik Jung, Hee-Young Park, Yung-Eun Sung ,1
School of Chemical & Biological Engineering and Research Center for Energy Conversion & Storage, Seoul National University, Seoul 151-744, South Korea Received 7 September 2006; received in revised form 14 December 2006; accepted 15 December 2006 Available online 21 January 2007

Abstract Pt-modied Au nanoparticles on carbon support were prepared and analyzed as electrocatalysts for methanol electro-oxidation. In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and Pt-modied Au nanoparticles, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles (3.5 nm diameter), Au nanoparticles were supported spontaneously on the surface of carbon black in the aqueous solution. Then a nanoscaled Pt layer was deposited on the surface of carbon-supported Au nanoparticles by the chemical reduction. The structural information and electrocatalytic activities of the Pt-modied Au nanoparticles were conrmed by transmission electron microscopy (TEM), X-ray diffractometry (XRD) and cyclic voltammetry (CV). The results indicate that carbon-supported Au nanoparticles were modied with the reduced Pt atoms selectively. The Pt-modied Au nanoparticles showed the higher electrocatalytic activity for methanol electro-oxidation reaction than the commercial one (JohnsonMatthey). The increased electrocatalytic activity might be attributed to the effective surface structure of Pt-modied Au nanoparticles, which have a high utilization of Pt for surface reaction of methanol electro-oxidation. 2007 Elsevier Ltd. All rights reserved.
Keywords: Direct methanol fuel cell; Electrocatalyst; Successive reduction process; Pt-modied Au nanoparticles; Methanol electro-oxidation

1. Introduction Direct methanol fuel cells (DMFCs) have been considered the ideal fuel cell system for fuel cell-based mobile power supply systems. Indeed, there are certain advantages to be found in the use of methanol as fuel, not the least of which is its high energy density and the fact that it stays in liquid state at room temperature [1,2]. However, there are some unsolved technical problems involved in the commercialization of DMFCs: the high loading of noble metal electrocatalysts, the slow kinetics of electrode reaction and the crossover of methanol through the membrane, etc. The most serious problem is the high loading of Pt and its alloy electrocatalysts. Much effort has been devoted to increasing electrocatalytic activity and reducing the loading of noble metal catalysts [311].

Corresponding author. Tel.: +82 2 880 1889; fax: +82 2 888 1604. E-mail address: ysung@snu.ac.kr (Y.-E. Sung). ISE member.

Since electrocatalytic reactions are strongly dependent on the surface structure of metal catalysts, the atom-leveled design of the surface structure plays a signicant role in a high catalytic activity and the utilization of electrocatalysts. Therefore, surface-modied electrocatalysts have attracted much attention due to their unique structure and new electronic and electrocatalytic properties [1215]. Various methods can be employed in preparing the surface-modied nanoparticles, such as underpotential deposition (UPD) [1623], thermal treatment approach [24], spontaneous formation [2528], and successive reduction process [29,30]. Recently, the nanoparticles with uniform Pt-group overlayers (down to 12 monolayers) were prepared with the UPD approach and applied for the oxygen reduction [1922] and methanol oxidation [23]. Although the UPD redox replacement technique offers many interesting results, the chemical approaches are important for the practical application of surfacemodied electrocatalysts. The low-priced and high catalytic activated electrocatalysts can be prepared if highly dispersed nanoparticles are used as a substrate for depositing the elec-

0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2006.12.068

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trocatalytic active materials with the chemical methods. Zhao and Xu reported the preparation of Pt-modied Au nanoparticles by using an aqueous hydrogen reduction method [30]. The utilization of prepared Pt was nearly 100%, which is remarkable result. However, the Au nanoparticles (10 nm diameter) were too big to obtain a high specic surface area for depositing the active elements. Therefore, the highly dispersed metallic substrate is a prerequisite for obtaining a high catalytic activity of surface-modied electrocatalysts. In the present experiment, the carbon-supported 3.5 nm Au nanoparticles were adapted as the substrate and the successive reduction process was used for depositing Pt on the surface of Au nanoparticles. The merits of gold nanoparticle as a metal substrate for catalyst design is its ability to prepare routinely mono-dispersed colloid nanoparticles having a wide diameter range and good stability in the acid electrolytes [30,31]. The prepared electrocatalysts were extended for electrocatalytic applications. The central point of this study is the application of carbon-supported and highly dispersed Au nanoparticles for the preparation of surface-modied electrocatalysts. 2. Experimental 2.1. Preparation of carbon-supported and Pt-modied Au nanoparticles All aqueous solutions were made with deionized (DI) water, which was further puried with a Milli-Q system (Millipore water, 18.2 M cm). The following materials were obtained from Aldrich: HAuCl4 3H2 O, H2 PtCl6 xH2 O, sodium citrate tribasic dihydrate (Na3 C6 H5 O7 2H2 O), NaBH4 and l-ascorbic acid (C6 H8 O6 ). All chemicals were of analytical grade and were used as received. The carbon-supported 30 mass% Au nanoparticles (30AuC) were synthesized as follows (the gold nanoparticles used in this study were prepared as described in detail elsewhere [22]): rst, Au nanoparticles of ca. 3.48 nm diameter were prepared by adding HAuCl4 3H2 O (0.0579 g) to 800 ml of H2 O with vigorous stirring, followed by the addition of aqueous sodium citrate (0.1 g) 1 min later. After an additional minute, NaBH4 (0.03 g) and sodium citrate (0.1 g) dissolved solution was added. The solution was stirred for 30 min, and then adequate carbon black (Vulcan XC-72R, 0.0672 g) was added. During the stirring for 48 h, gold colloid particles were supported spontaneously on the surface of the carbon black particle. After supporting Au nanoparticles on the surface of the carbon black particles, the red color of the solvent changed to a transparent color. The mass percent of Au in the 30AuC was optimized experimentally by trial and error. Generally, the optimum mass percent of spontaneously supported metal nanoparticles is dependent on the specic surface area of support due to the nite size of particle and interparticle repulsion [22,32]. The cleaning process of the solution was conducted by precipitation and decantation. The preparing procedures of Pt-modied Au nanoparticles on carbon support were as follows: rst, an adequate amount of Pt precursor solution was added to 400 ml of the as-prepared

30AuC-dispersed solutions. Next, an adequate amount of ascorbic acid solution was added [29]. After stirring for 20 h, the resultant solution was precipitated, washed and dried in the vacuum oven at 350 K. The prepared electrocatalysts were coded as AuPt[x], x denoting the atomic Pt/Au ratio within the nanoparticles. The characteristics of Au-Pt[x] electrocatalysts were also compared with the 40 mass% Pt/C (JohnsonMatthey, PtC[JM]). 2.2. Catalyst characterization Samples for TEM were prepared by placing a drop of solution onto a carbon-coated copper grid and were examined using a JEOL 2010 transmission electron microscopy operated at 200 kV. Analysis of X-ray diffraction was performed with Rigaku D/MAX 2500 operated with a Cu K source ( = 1.541 A) at 40 kV and 100 mA. 2.3. Electrochemical measurement Cyclic voltammogram was obtained in a conventional threeelectrode electrochemical cell using glassy carbon electrode (6 mm diameter) as the working electrode, platinum wire as the counter electrode and saturated calomel electrode (SCE) as the reference electrode. Electrochemical measurements were all recorded and reported versus normal hydrogen electrode (NHE). The glassy carbon electrode was polished with 1, 0.3, 0.05 m-Al2 O3 slurry and washed ultrasonically with Millipore water before use. The catalyst inks were prepared by mixing carbon-supported catalysts, Millipore water, a 5 wt.% Naon solution (Aldrich Chem. Co) as the binding material and 2-propanol (JUNSEI). The 200 l of Millipore water, 572 l of Naon solution and 8 ml of 2-propanol per 0.1 g of catalysts were mixed and then stirred until ink had formed homogeneously. The catalyst ink was dropped on the glassy carbon electrode with a micropipette, and the carbon electrode was then dried in a vacuum oven. Electrochemical experiments were performed with an AUTOLAB (Eco Chemie). Solutions of 0.5 M H2 SO4 and 1 M CH3 OH/0.5 M H2 SO4 were purged with nitrogen gas prior to measuring. In order to identify the surface composition and activities of the carbon-supported electrocatalysts, voltammetry was conducted in the potential between 0.051.5 V versus NHE at a scan rate of 20 mV/s. Prior to the measurement of carbon-supported electrocatalysts, the cyclic voltammetry was conducted with a scan rate of 50 mV/s as the cleaning step of electrode in the solution of 0.5 M H2 SO4 . 3. Results and discussion 3.1. TEM analysis The Pt-modied Au nanoparticles on carbon support were characterized by HRTEM [33]. The surface-averaged dispersion, D (ratio of atoms that are on the surface to the total number of atoms in the particle), was calculated according to

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the following equation: D=6 v s


2 i n i di 3 i n i di

(1)

where ni is the frequency of the occurrence of particles of the size di ; v the volume per metal atom in the bulk; s is the average area occupied by a metal atom on the surface. The prefactor 6 is valid for spherical particles. For determining the particle size distribution from low-magnication images, all particles were regarded as spherical. Fig. 1(a) shows an image of the highly dispersed Au nanoparticles on the carbon black. The dispersion and mean particle diameter of carbon-supported Au nanoparticles were 0.2936 and 3.48 nm, respectively. Fig. 1(b) and (c) shows the TEM images of AuPt[0.5] and AuPt[1.0], respectively. In the Pt-modied Au nanoparticles on carbon support, the high

dispersion and similar surface particle coverage as 30AuC were sustained. Particle size distributions were compared in Fig. 1(d). The mean particle diameters were increased and the widths of distributions were narrowed according to the increased amount of Pt. The decreased widths of distributions indicate that no new additional nucleation took place on the surface of the carbon black particles during the formation of Pt-modied Au nanoparticles, and the growth rates of the nanoparticles were more rapid in the small particles than in the large ones. The increased size of the resultant nanoparticles with the increased amount of Pt is in agreement with the increase expected from the following equation: DAuPt[x] = DAu 1 + Vm (Pt)[Pt] Vm (Au)[Au]
1/3

(2)

Fig. 1. TEM images and particle size distributions of Pt-modied Au nanoparticles on carbon support: (a) TEM image of carbon-supported Au nanoparticles, (b) TEM image of AuPt[0.5] nanoparticles, (c) TEM image of AuPt[1.0] nanoparticles, and (d) comparison of particle size distributions.

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Fig. 2. Comparison of experimental and calculated diameters in the Pt-modied Au nanoparticles.

Fig. 3. X-ray diffraction proles of Pt-modied Au nanoparticles.

where Vm is the mole volume; [ ] the overall concentration of the two metals involved; DAuPt[x] the diameter of the Pt-modied Au particles; DAu is the diameter of the carbon-supported Au particles [29]. Fig. 2 shows the relation between the experimental and calculated diameters, and the mean particle sizes

are given in parentheses. The experimental diameters of the Pt-modied Au nanoparticles were corresponded to the diameter which was obtained from the calculation, although an error range was detected. In this study, the experimental diameters of 30AuC, AuPt[0.5] and AuPt[1.0] are 3.48, 3.80 and 4.55 nm,

Fig. 4. (a) Cyclic voltammograms in 0.5 M H2 SO4 , (b) mass-specic Au surface area (m2 /gAu ) and exposed Au site percentages (%), and (c) mass-specic Pt Au areas (m2 /gPt ) and (m2 /gtotal metal ). Current densities vs. potential plots were measured in 0.5 M H2 SO4 at room temperature. Pt Pt

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respectively. The particle size of AuPt[1.0] suggests that the thickness of the deposited Pt layer is 0.535 nm and corresponds to about 1.5 atomic layer for the Pt atom (that is, dPt = 0.36 nm) [30,34]. These results indicate that the reduced Pt atoms were deposited selectively on the surface of carbon-supported Au nanoparticles. 3.2. XRD analysis For obtaining the crystallographic information, an XRD measurement was conducted. The wide-range XRD proles showed the main peaks of crystalline Au nanoparticles. The main peaks of Au nanoparticles occurred at 38.18 (1 1 1), 44.39 (2 0 0), 64.58 (2 2 0) and 77.55 (3 1 1). This result indicates that the Au nanoparticles present stably in the Pt-modied Au nanoparticles. The short-range XRD proles are shown in Fig. 3. As shown in Fig. 3, a change in the main peaks are noticeable from the AuPt[0.75] onward. That is, another peak appeared between (1 1 1) main peaks of the Au and Pt nanoparticles. This might be due to the modied structure of Au nanoparticles with Pt. The further analysis has to be performed for the exact identication of Pt phase in the Pt-modied Au nanoparticles.

3.3. CV characteristics The surface structures of bimetallic nanoparticles can take various and complex shapes [35]. Analyzing the surface composition is very important since the Au nanoparticles were modied with the Pt atoms, and the catalytic reactions are sensitive to the surface structure. Cyclic voltammetry was performed with solutions of 0.5 M H2 SO4 for obtaining the surface composition and characteristics of surface-modied nanoparticles, and the results are represented in Fig. 4. Fig. 4(a) shows the cyclic voltammogram, and the y-axis represents the mass-specic current density (A/gAu ). The reduction of Au oxide (1.2 V) and Pt oxide (0.7 V) are shown in Fig. 4(a). A modication of the surface composition occurred in conjunction with the increased Pt. That is, the reduction current of Au oxide decreased while the reduction current of Pt oxide increased as the amount of Pt increased. This result suggests that the reduced Pt atoms were deposited on the surface of the Au nanoparticles selectively. From the charge of the oxide reduction peak in the negative-going scan, the real surface area of nanoparticles was determined as follows: 400 C cm2 for Au and 440 C cm2 for Pt [36,37]. Friedrich et al. insisted that the determination of the real surface area from oxide reduc-

Fig. 5. Electrocatalytic activity of Pt-modied Au nanoparticles on carbon support for methanol electro-oxidation: (a) current densities (A/gtotal metal ) vs. potential plots, (b) current densities (A/gPt ) vs. potential plots, and (c) mass-specic current densities at 0.6 V vs. NHE. Current densities vs. potential plots were measured in 0.5 M H2 SO4 + 1 M CH3 OH at room temperature.

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tion is more practical than from hydrogen desorption because of the higher charges involved [36]. The exposed Au site percentages Au (%) were calculated according to the following equation: Au (%) = AAu /gAu 100 A0 /gAu Au (3)

4. Conclusions The Pt-modied Au nanoparticles on carbon support were prepared by a successive chemical reduction process. As indicated by the TEM and XRD analysis, the successively reduced Pt atoms were deposited on the surface of Au nanoparticles selectively. From the CV analysis, the reduction current of Au oxide decreased while the reduction current of Pt oxide increased according to increased Pt. In other words, the surface structure of Au nanoparticles was modied by successive reductions of Pt element. The Pt-modied Au nanoparticles on carbon support represented the similar catalytic activity with the commercial pure Pt electrocatalysts by using a smaller amount of Pt. This increased catalytic activity might be attributed to the high utilization of Pt atoms for the electrocatalytic reaction. By using carbon-supported nanoparticle substrate and the successive chemical reduction method, a high performance electrode with a small amount of Pt could be prepared and readily applied to other electrocatalytic reactions, as well as to the methanol electro-oxidation reaction. Acknowledgements This work was supported by the Ministry of Commerce, Industry and Energy, the KOSEF through the Research Center for Energy Conversion & Storage and the Korea Research Foundation (Grant #KRF-2004-005-D00064). References

where AAu /gAu and A0 /gAu are mass-specic Au surface areas Au in the AuPt[x] and 30AuC, respectively. For the calculation of mass-specic active areas, Pt and Au masses were estimated from the used amount of electrocatalysts on the basis of assumption. Mass-specic Au surface areas are shown in Fig. 4(b) and exposed Au site percentages are given in parentheses. As noted in Fig. 4(b), the surface area of 30AuC was 22.7 m2 /g, and the exposed Au site percentage of AuPt[1.0] was 7.40. This result indicates that the Au nanoparticles were coated by the reduced Pt atoms partially, and a Pt skin-like surface structure was present in the AuPt[1.0] electrocatalyst. In addition, the mass-specic active areas were calculated from the reduction area of Pt oxide, as shown in Fig. 4(c). The lled squares and empty circles represent the mass-specic Pt surface area in terms of Pt and total metal weights, respectively. The m2 /gPt increased Pt as the amount of Pt decreased. The m2 /gPt of AuPt[0.25] was Pt 207.9 m2 /g and this active area corresponded to 88.4% of Pt utilization [30]. In the m2 /gtotal metal , the AuPt[0.75] showed the Pt highest value in the prepared electrocatalysts. In other words, the AuPt[0.75] had the most efcient surface structure for the surface electrocatalytic reaction. 3.4. Methanol electro-oxidation The catalytic activity of Pt-modied Au nanoparticles for methanol electro-oxidation reaction was measured by obtaining a voltammogram in the solution of 1 M CH3 OH/0.5 M H2 SO4 . As shown in Fig. 5(a) and (b), the reported current here was normalized to the amount of total metal and Pt, respectively. For the calculation of mass specic current densities, Pt and Au masses were estimated from the used amount of electrocatalysts on the basis of assumption. Fig. 5(c) showed the mass-normalized currents, which were obtained at 0.6 V versus NHE. The empty circle represents the current density in terms of total metal content. The measured mass-specic activity of PtC[JM] was 17.87 A/g [38]. The Pt-modied Au nanoparticles showed as much catalytic activity as the commercial one, while AuPt[0.75] showed the highest relative activity at 0.6 V. This demonstrates that similar catalytic activity was obtained in the Pt-modied Au nanoparticles by using a smaller amount of Pt. This trend corresponds to that of m2 /gtotal metal . The lled squares represent the current denPt sity in terms of the Pt amount and show that the catalytic activities increased as the loading amount of Pt decreased. Most notably, the AuPt[0.25] showed about a 250% increase in catalytic activity compared to that of the commercial one. This distinction might be due to the effective surface structure of Pt-modied Au nanoparticles for the electrocatalytic reaction.

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