Electrochimica Acta 52 (2007) 58735878

A new route for the electrodeposition of platinumnickel alloy nanoparticles on multi-walled carbon nanotubes
Yue Zhao a , Yifeng E a , Louzhen Fan a, , Yongfu Qiu b , Shihe Yang b,
b

Department of Chemistry, Beijing Normal University, Beijing 100875, China Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China Received 8 December 2006; received in revised form 2 February 2007; accepted 6 March 2007 Available online 12 March 2007

Abstract An electrochemical method was developed to deposit platinum (Pt) and nickel (Ni) nanoparticles on multi-walled carbon nanotubes (MWCNTs) through a three-step process. X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX) show the alloy formation for Pt and Ni with a ratio of 1:1. The presence of Pt(0), Ni(0), Ni(OH)2 , NiOOH and slight NiO was deduced from XPS data. Electrocatalytic properties of the resulting PtNi/MWCNT electrode for methanol oxidation reaction were investigated. Compared with Pt/MWCNT, an appreciably improved resistance to CO poisoning was observed for the PtNi/MWCNT electrode, which was interpreted by a mechanism based on the bifunctional catalysis. The successful preparation of PtNi/MWCNT nanocomposites opens a new path for an efcient dispersion of the promising electrocatalysts in the direct methanol fuel cells. 2007 Elsevier Ltd. All rights reserved.
Keywords: Electrodeposition; Platinumnickel alloy; MWCNT; Electrocatalyst; Methanol oxidation

1. Introduction The direct methanol fuel cells (DMFCs) have received considerable attentions for applications in transportation, portable electronics, and residential power sources, due to their high energy density, relatively low operating temperatures, zero or low emission of pollutants, and minimal corrosion problems. However, the commercial viability of DMFCs is still hindered by several factors, including the low catalytic activity of electrodes both for the oxygen reduction reaction (ORR) and for the methanol oxidation reaction, the high costs of the Pt-based electrocatalysts, and the susceptibility of the catalysts to be poisoned by the CO-like intermediates formed in the methanol oxidation reaction [15]. The most common solution to these problems is to employ bi- or tri-metallic catalysts that combine platinum with other metals such as Ni, Co, etc., and disperse the metals nely on proper supports [6]. Over the last two decades, various Pt-based bimetallic catalysts have been studied [710]. Among them, PtNi bimetallic

Corresponding author. Fax: +86 10 58802075. Corresponding author. E-mail addresses: lzfan@bnu.edu.cn (L. Fan), chsyang@ust.hk (S. Yang).

catalyst has attracted more interests [1117]. Ni alloying with Pt can improve the methanol oxidation by lowering the electronic binding energy in Pt. In addition, the presence of Ni oxides in the catalyst provides an oxygen source for CO oxidation at lower potentials. On the other hand, the PtNi alloy also presents an improved activity for the oxygen reduction than Pt alone by reducing the cell voltage when used as a cathode. In order to enhance the catalytic activity of the PtNi alloy, two major issues need to be considered concerning the extent of dispersion and the nature of support such as multi-walled carbon nanotubes (MWCNTs). As a new form of carbon, MWCNTs have been regarded as a new support for metal catalysts due to their small size, high chemical/thermal/mechanical stabilities and large surface area to volume ratio [1822]. At present, high surface area noble metal electrodes have been successfully prepared via several routes [17,2325]. However, electrodeposition of PtNi alloy nanoparticles on carbon nanotubes has not been achieved so far. Considering the advantages of electrodeposition, such as high purity of deposits and simple procedure of deposition, herein we suggest a new approach based on a so-called three-step process to deposit PtNi alloy nanoparticles on MWCNTs. The resulting PtNi/ MWCNT catalysts have been characterized by transmission

0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2007.03.020

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electron microscope (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The electrocatalytic properties of the PtNi/MWCNT electrode have been investigated by cycle voltammetry (CV) method. 2. Experimental 2.1. Materials Multi-walled carbon nanotubes (MWCNTs) were purchased from Shenzhen Nanotech. Port. Co., Ltd., Shenzhen, China, and further puried prior to use by stirring in concentrated nitric acid for 12 h. Toluene (C6 H5 CH3 ) (Park Co., Dublin, Ireland) was dried with sodium and reuxed for 6 h before distillation and then stored in the present of sodium. Other reagents are as follows: potassium sulfate (K2 SO4 ) (A.R., Nacalai Tesque, Inc., KYOTO, Japan); potassium tetrachloroplatinate (II) (Cl4 K2 Pt) (99.9%-Pt, International Laboratory, USA); nickel (II) chloride hexahydrate (NiCl2 6H2 O) (98%-Ni, SigmaAldrich Laborchemikalien GmbH, Germany); sulfuric acid (H2 SO4 ) (A.R., BeiHua, Inc., Beijing, China) and ethanol (CH3 CH2 OH) (A.R., Chemical Reagent, Inc., Tianjin, China). Deionized water (20 1 C, pH 7, = 18.3 M /cm) was puried by passing through an EASY pure compact ultrapure water system (Barnstead Co., USA). 2.2. Electrode preparation The glassy carbon (GC) electrode (3 mm diameter) was polished to a mirror nish with emery paper and alumina slurry (1.0 m, 0.3 m), and ultrasonically cleaned in toluene for a few minutes, then dried with a high-purity nitrogen stream immediately before use. One milligram puried MWCNTs was dispersed in 10 ml toluene by ultrasonication for 30 min to give a 0.1 mg/ml suspension. Fifteen microlitres of the suspension was directly cast on GC electrode surface and evaporated in the solvent at room temperature to prepare the MWCNTs lm modied electrode. 2.3. Measurements A conventional cell with a three-electrode conguration was used throughout this work. The MWCNTs/GC electrode was employed as the working electrode, a platinum wire served as the counter electrode and a Ag/AgCl electrode was used as the reference electrode. Electrochemical measurements were performed with a CHI705A (CH Instruments, Inc., USA) electrochemical analyzer and the potentials were measured and reported with respect to the Ag/AgCl electrode. Morphologies of the as-synthesized PtNi/MWCNTs were examined on a Hitachi 600 transmission electron microscope (TEM), which was operated at 300 kV. X-ray photoelectron spectroscopy data were obtained with an ESCALab220i-XL electron spectrometer from VG Scientic using 300 W Al K radiation. The base pressure was about 3 109 mbar. The bind-

ing energies were referenced to the C1s line at 284.8 eV from adventitious carbon. 3. Results and discussion 3.1. Physical characterization and structural studies A good dispersion of the catalyst on the carbon support is a precondition for attaining good electrocatalytic activity in a fuel cell reaction. Fig. 1 shows the typical TEM image of MWCNTs after electrochemical deposition. A homogeneous dispersion of nanoparticles largely spherical in shape and approximately 10 nm in size can be observed. From the energy dispersive Xray spectroscopy (EDX) of this sample (Fig. 2), it can be seen that Pt and Ni are the major elements with an atomic ratio of approximately 1:1. XRD analyses demonstrate the characteristic peaks of the Pt fcc structure (see Fig. 3). For PtNi/MWCNT (curve a in Fig. 3), no peaks for fcc Ni are observed, but the 2 of (1 1 1) peak has angle shift from 39.84 of Pt/MWCNT (curve b) to 40.48. The angle shifts of the Pt peaks are the indication for the alloy formation between Pt and Ni [26], which is the evidence that the PtNi alloy nanoparticles are successfully deposited on MWCNTs. To investigate the chemical nature of these PtNi alloy nanoparticles, XPS analyses were performed. Spectra of Pt 4f and Ni 2p are shown in Fig. 4a and b, respectively. The Pt 4f7/2 and 4f5/2 lines appear at 70.91 eV and 74.13 eV, respectively, with the theoretical ratio of peak areas of 4:3. The peaks for Pt2+ and Pt4+ at 73.8 eV and 74.6 eV, respectively, were not found, indicating that Pt is present in the zero-valent metallic state in

Fig. 1. A typical TEM micrograph of the electrode after electrodeposition.

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Fig. 2. EDX spectrum of PtNi/MWCNT.

the nanoparticles. In contrast, the Ni 2p3/2 spectrum shows a complex structure with intense satellite signals of high binding energy adjacent to the main peaks, which may be ascribed to a multielectron excitation (shake-up peaks) (Fig. 4b). Curve tting of the Ni 2p3/2 signals gives different nickel species. After considering the shake-up peaks, the Ni 2p3/2 XPS peaks at the binding energies of 852.6 eV, 854.0 eV, 855.8 eV, and 857.1 eV are ascribed to Ni(0), NiO, Ni(OH)2 , and NiOOH, respectively [26]. Furthermore, with reference to pure Pt, the Pt 4f XPS spectrum of PtNi on MWCNT experiences peak shifts of 0.29 eV and 0.30 eV for Pt 4f7/2 (71.20 eV for pure Pt) and Pt 4f5/2 (74.53 eV), respectively, indicating an electronic structural change of Pt when it is alloyed with Ni. Most likely, Ni(0) occupies the platinum lattice, and the metallic grains are intermixed with amorphous Ni oxides, such as NiO, Ni(OH)2 and NiOOH revealed in the XPS spectra. 3.2. The formation of PtNi/MWCNT The electrochemical deposition of PtNi nanoparticles on MWCNTs was carried out by making use of an established three-step process [2729] but with important improvement (as
Fig. 4. X-ray photoelectron spectra of (a) Pt 4f and (b) Ni 2p of PtNi/MWCNT electrode.

Fig. 3. XRD analysis of PtNi/MWCNT (a) and Pt/MWCNT (b).

shown in Scheme 1): (1) generation of oxide functional groups (quinoid, carbonyl and carboxyl) at the defect sites located at the ends and/or the sidewalls of the carbon nanotubes by potential cycling (200 mV s1 ) from +1.8 V to 0.4 V in 0.5 M K2 SO4 solutions for 10 min; (2) oxidation of PtCl4 2 and Ni2+ to complexes of Pt(IV) and Ni(III) on the MWCNT surface from K2 PtCl4 + NiCl2 + 0.1 M K2 SO4 (pH 4) aqueous solutions by potential-step method. The potential was increased from 0.3 V to 1.3 V with pulse width of 0.001 s and this was carried out successively until a steady pulse current reached; (3) conversion of the surface complexes on the MWCNTs to platinum and nickel nanoparticles through potential cycling from +1.0 V to 0.26 V in 0.1 M H2 SO4 solutions to the steady state. In order to investigate the oxidation of PtCl4 2 and Ni2+ to complexes of Pt(IV) and Ni(III) on the MWCNT surface, cyclic voltammogram of MWCNT/GC (pre-treated in K2 SO4 solution) in 2 M K2 PtCl4 + 1 M NiCl2 + 0.1 M K2 SO4 was obtained (Fig. 5). The lower limit of the potential scan was restricted to +0.3 V in order to prevent the electrodeposition of Pt(0) or Ni(0) from the solution. Two irreversible anodic peaks are observed. The peak at 1.05 V corresponds to the oxidation of PtCl4 2 to Pt(IV) complex. As reported, the oxygen atom from func-

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Scheme 1. Schematic illustration of the three-step process for electrochemical synthesis of PtNi/MWCNTs.

tional groups such as quinoid, carbonyl and carboxyl, which were generated on the surfaces of MWCNTs during electrochemical pre-treatment, serves as one of the two axial ligands when the planar complex of Pt(II) is oxidized to form the octahedral complex of Pt(IV) [2729]. Another irreversible anodic peak at 0.92 V is relative to the oxidation of Ni2+ to Ni(III) complex, which is in accord with a previous work [3032]. Therefore, it is reasonable to believe that in our three-step process, the complexes of Pt(IV) and Ni(III) were the precursors of PtNi nanoparticles on the MWCNTs, which were then obtained by potential scanning in 0.1 M H2 SO4 solution in the potential range from +1.0 V to 0.26 V to steady state. It has been reported that electrochemical pre-treatments of electrode surfaces result in a pronounced enhancement for the electrodeposition of Ni-containing species such as Ni(OH)2 and NiOOH [26,33,34]. Clearly, the electrodeposition of the Ni-containing species is necessarily accompanied by the precipitation of OH ions generated at the electrode surface by in situ electrochemical reduction of adsorbed oxygen-containing species. Our previous work has demonstrated the formation of oxide functional groups (carbonyl, hydroxyl and carboxyl) on the surfaces of MWCNTs by electrochemical pre-treatments

[29]. We believe that the production of Ni(OH)2 and NiOOH are somehow related to the electrochemical process for the oxide functionalization of MWCNTs. As for NiO, it is known to be formed in very small amount by electrochemical treatment and related to surface passivation of the electrode [26]. Probably, these Ni-containing species are nely dispersed and inter-mixed with the PtNi nanoparticles. 3.3. Activity for oxygen reduction and methanol oxidation For comparison, Pt/MWCNT was also obtained under the same experimental conditions as PtNi/MWCNT except that no NiCl2 was used for the second step. Fig. 6 shows the cyclic voltammograms of the resulting PtNi/MWCNT (curve a) and Pt/MWCNT (curve b) in 0.1 M H2 SO4 . It can be seen that the reversible hydrogen adsorption/desorption peaks between 0.25 V and 0.1 V and preoxidation/reduction between 0.4 V and 1.0 V of the Pt surface are clearly seen for Pt/MWCNT, indicating the presence of Pt, whereas for the PtNi/MWCNT, the current densities associated with the reversible hydrogen adsorption region have decreased due to the site blocking effect [35], suggesting that the high dispersion of the PtNi alloy nanoparti-

Fig. 5. Cyclic voltammograms of MWCNT/GC electrode in 2 M K2 PtCl4 + 1 M NiCl2 + 0.1 M K2 SO4 (pH 4) solution (scan rate: 100 mV s1 ).

Fig. 6. Cyclic voltammograms of PtNi/MWCNT (a) and Pt/MWCNT (b) electrodes in 0.1 M H2 SO4 solution (scan rate: 100 mV s1 ).

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Fig. 7. Cyclic voltammograms of PtNi/MWCNT (a) and Pt/MWCNT (b) electrodes in 2 M CH3 OH + 0.1 M H2 SO4 solution (scan rate: 100 mV s1 ).

Fig. 8. Currenttime plots of (a) PtNi/MWCNT and (b) Pt/MWCNT electrodes in 2 M CH3 OH + 0.1 M H2 SO4 solutions with a constant potential of 0.66 V vs. Ag/AgCl.

cles with a disordered surface structure was obtained and that no surface enrichment of platinum was found. Signicantly, it can be observed that the onset of the oxide formation and the peak potential of oxide reduction are shifted to more positive positions by 20 mV and 70 mV, respectively, indicating that the alloying of Pt with Ni inhibits the chemisorption of OH on the Pt sites at potentials above 0.6 V. This may have a benecial effect on the oxygen adsorption at low overpotentials, and thus may lead to the enhancement of the ORR kinetics [21,36]. The catalytic activity of PtNi/MWCNT catalyst was also measured in the oxidation of methanol, which is a useful application in the direct methanol fuel cell (DMFC). Fig. 7 shows typical CVs of PtNi/MWCNT electrode (curve a) and Pt/MWCNT electrode (curve b). Notably, the shapes of the CV curves and peak potentials are in line with other works typically using Pt electrode, but the onset potential for methanol oxidation for PtNi/MWCNT electrode occurs at an anodic potential 0.26 V, which is about 50 mV lower than that for Pt/MWCNT (0.31 V). The current with the alloy electrode is also smaller than with the Pt electrode, which can be explained by the smaller amount of Pt in the alloy electrode. On the other hand, the ratio of the forward anodic peak current (If ) to the reverse anodic peak current (Ib ) can be used to describe the catalyst tolerance to carbonaceous species accumulation [37]. Ordinarily, If /Ib can be used as a performance index of a catalyst for the conversion and a higher If /Ib value implies better oxidation of methanol to CO2 . In our experiments, the ratio was estimated to be about 2.0 for the PtNi/MWCNT electrode, even higher than the value of 1.4 for the Pt/MWCNT electrode. Such a high value for PtNi/MWCNT electrode indicates that most of the intermediate carbonaceous species were oxidized to CO2 in the forward scan, suggesting that the interaction of Pt and Ni leads to the less poisoning of Pt by the CO-like intermediates formed during methanol activation. The current densitytime plots of PtNi/MWCNT and Pt/MWCNT electrodes in 2.0 M CH3 OH + 0.1 M H2 SO4 at 0.66 V (versus Ag/AgCl) for 3600 s were further measured. Fig. 8 shows such typical it plots with the current normalized to the initial current (i/i0 ) to indicate the fractional decay with time. Pure Pt is easily poisoned by CO-like intermediates

formed during methanol activation. The current decay was rapid for Pt/MWCNT electrode (curve b), reaching 45% of the initial current in 10 min and 30% of the initial value in an hour. This means that for Pt/MWCNT, 70% of the Pt surface active sites were lost after 1 h. In contrast, for PtNi/MWCNT electrode (curve a), 75% of initial current in 10 min and 68% of initial current after 1 h were retained, which suggests that pairing the Ni with Pt decreases the opportunity of Pt poisoning. According to the bifunctional catalysis, the mechanism is explained as follows: from XPS data, the alloy sites consisted mainly of metallic Pt and Ni(II). Pt(0) is the initial active site for the CH bond cleavage in methanol adsorbed on its surface, while Ni(II) is the neighboring site providing mobile oxygen species for the oxidation of Pt-bonded CO to form CO2 [38]. The cooperative action between Pt and Ni (with different oxidation states) in the removal of adsorbed CO intermediates releases the Pt sites for the next round of action. Therefore, the interface between Pt and Ni is of utmost importance in the catalysis of methanol electrooxidation, which increases the resistance of the Pt catalysts to CO poisoning (as shown in Fig. 7) and then extends its lifetime (as shown in Fig. 8). 4. Conclusion This work suggests a new route of electrodepositing PtNi alloy nanoparticles on MWCNTs. On the basis of the characterizations by TEM, EDX, XRD and XPS, the as-prepared PtNi nanoparticles on the surface of MWCNT consist of 1:1 PtNi alloy containing mainly Pt(0) and Ni(0), Ni(OH)2 , NiOOH and a minor amount of NiO. The PtNi/MWCNTs were used as electrocatalysts for the oxidation of methanol and were compared with that of Pt/MWCNT. Cyclic voltammetry showed that the PtNi/MWCNT has a benecial effect on the oxygen adsorption at low overpotentials, and has a higher If /Ib value than Pt/MWCNT in methanol solution. The increased resistance to CO poisoning of Pt is attributed to effectiveness of the neighboring Ni sites in removing the reaction intermediates. Further studies are warranted to understand the detailed deposi-

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Y. Zhao et al. / Electrochimica Acta 52 (2007) 58735878 [14] M.K. Min, J. Cho, K. Cho, H. Kim, Electrochim. Acta 45 (2000) 4211. [15] M.T. Paffet, G.J. Beery, S. Gottesfeld, J. Electrochem. Soc. 135 (1988) 1431. [16] K.T. Kim, Y.G. Kim, J.S. Chung, J. Electrochem. Soc. 142 (1995) 1531. [17] T. Toda, H. Igarashi, H. Uchida, M. Watanabe, J. Electrochem. Soc. 146 (1999) 3750. [18] J. Li, A. Cassell, L. Delzeit, J. Han, M. Meyyappan, J. Phys. Chem. B 106 (2002) 9299. [19] G. Tamizhmari, G.A. Capuano, J. Electrochem. Soc. 141 (1994) 968. [20] U.A. Paulus, A. Wokaun, G.G. Scherer, T.J. Schmidt, V. Stamenkovic, N.M. Markovic, P.N. Ross, J. Phys. Chem. B 106 (2002) 4181. [21] V. Stamenkovic, T.J. Schmidt, P.N. Ross, N.M. Markovic, J. Phys. Chem. B 106 (2002) 11970. [22] E. Antoli ni, R.R. Passos, E.A. Ticianelli, Electrochim. Acta 48 (2002) 263. [23] J. Shim, D.Y. Yoo, J.S. Lee, Electrochim. Acta 45 (2000) 1943. [24] N.J. Alonso-Vante, Chem. Phys. 93 (1996) 702. [25] Y. Xing, J. Phys. Chem. B 108 (2004) 19255. [26] G. Casella, M.R. Guascito, M.G. Sannazzaro, J. Electroanal. Chem. 462 (1999) 202. [27] D.J. Guo, H.L. Li, J. Electroanal. Chem. 573 (2004) 197. [28] L. Xu, F.L. Li, S.J. Dong, J. Electroanal. Chem. 383 (1995) 133. [29] Y. Zhao, L.Z. Fan, H.Z. Zhong, Y.F. Li, S.H. Yang, Adv. Funct. Mater., 2007, in press. [30] S. Bruckenstein, M.J. Shay, Anal. Chem. 188 (1985) 131. [31] H. Angerstein-Kozlowska, B.E. Conway, A. Hamelin, L. Stoicoviciu, J. Electroanal. Chem. 228 (1987) 429. [32] H. Prakash, P. Natarajan, J. Photochem. Photobiol. A: Chem. 168 (2004) 81. [33] B. Wu, H. Lei, C. Cha, Y. Chen, J. Electroanal. Chem. 377 (1994) 227. [34] D. Rand, R. Woods, J. Electroanal. Chem. 31 (1971) 29. [35] J. Mathiyarasu, A.M. Remona, A. Mani, K.L. Phani, V.J. Yegnaraman, Solid State Electrochem. 8 (2004) 968. [36] A. Anderson, Electrochem. Acta 47 (2002) 3759. [37] Y. Lin, X. Cui, C. Yen, C.M. Wai, J. Phys. Chem. B 109 (2005) 14410. [38] F. Liu, J.Y. Lee, W. Zhou, J. Phys. Chem. B 108 (2004) 17959.

tion mechanism, optimize the electrocatalytic efciency, and tap the potential of this new catalyst dispersion/deposition method in the direct methanol fuel cells. Acknowledgments This work is nancially supported by National Natural Science Foundation of China (20473014), the Major State Basic Research Development Programs (2004CB719903) and NNSFC-RGC administrated by the UGC of Hong Kong (N HKUST604/04). References
[1] A. Arico, S. Srinivasan, V. Antonucci, Fuel Cells 2 (2001) 133. [2] J.S. Ye, H.F. Cui, Y. Wen, W.D. Zhang, G.Q. Xu, F.S. Sheu, Microchim. Acta 152 (2006) 267. [3] T.R. Ralph, M.P. Hogarth, Platinum Met. Rev. 46 (2002) 3. [4] S. Gottesfeld, I.D. Raistrick, S. Srinivasan, J. Electrochem. Soc. 134 (1987) 1455. [5] F. Freund, J. Lang, T. Lehman, K.A. Starz, Catal. Today 27 (1996) 279. [6] J.F. Drillet, A. Ee, J. Friedemann, B. Schnyder, V.M. Schmidt, Electrochim. Acta 47 (2002) 1983. [7] H.F. Cui, J. Ye, X. Liu, W.D. Zhang, Nanotechnology 17 (2006) 2334. [8] V. Jalan, E.J. Taylor, J. Electrochem. Soc. 130 (1983) 2299. [9] G.T. Glass, G.L. Cahen, G.E. Stoner, E.J. Taylor, J. Electrochem. Soc. 134 (1987) 58. [10] B.C. Beard, P.N. Ross, J. Electrochem. Soc. 137 (1990) 3368. [11] S. Mukerjee, S. Srinivasan, J. Electroanal. Chem. 357 (1993) 201. [12] S. Mukerjee, S. Srinivasan, M.P. Soriaga, J. Phys. Chem. B 99 (1995) 4577. [13] S. Mukerjee, S. Srinivasan, M.P. Soriaga, J. McBreen, J. Electrochem. Soc. 142 (1995) 1409.