Electrochemistry Communications 9 (2007) 20092012 www.elsevier.

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Ni hollow spheres as catalysts for methanol and ethanol electrooxidation

Changwei Xu
b

a,b,*

, Yonghong Hu a, Jianhua Rong a, San Ping Jiang b, Yingliang Liu

a,*

a Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632, China School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798, Singapore

Received 4 May 2007; received in revised form 18 May 2007; accepted 23 May 2007 Available online 9 June 2007

Abstract In this paper, we successfully synthesized Ni hollow spheres consisting of needle-like nickel particles by using silica spheres as template with gold nanoparticles seeding method. The Ni hollow spheres are applied to methanol and ethanol electrooxidation in alkaline media. The results show that the Ni hollow spheres give a very high activity for alcohol electrooxidation at a very low nickel loading of 0.10 mg cm2. The current on Ni hollow spheres is much higher than that on Ni particles. The onset potential and peak potential on Ni hollow spheres are more negative than that on Ni particles for methanol and ethanol electrooxidation. The Ni hollow spheres may be of great potential in alcohol sensor and direct alcohol fuel cells. 2007 Elsevier B.V. All rights reserved.
Keywords: Fuel cells; Alcohol electrooxidation; Ni; Hollow spheres

1. Introduction Direct alcohol fuel cells (DAFCs) based on liquid fuels such as methanol and ethanol have attracted enormous attention. Pt and Pt-based catalysts have been extensively investigated as the elctrocatalysts for the electrooxidation of liquid fuels such as methanol and ethanol [14]. However, the high price and limited supply of Pt constitute a major barrier to the development of DAFCs. The Pd, Au, Ag and Ni have been used as the electrocatalysts for alcohol oxidation [58]. The usage of Ni as the catalysts for alcohol electrooxidation is of interest as it is inexpensive metal. Here we successfully synthesized nickel hollow spheres and applied the nickel hollow spheres as the catalysts for methanol and ethanol oxidation in alkaline media.
Corresponding authors. Address: Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632, China (C. Xu). E-mail address: cwxuneuzsu@126.com (C. Xu). 1388-2481/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2007.05.028
*

Mesoscopic materials have become the focus of intensive research due to their fascinating electronic, mechanical, and chemical properties and have been extremely popular materials for electroanalysis and electrocatalysis [911]. Hollow spheres have attracted more attention due to their fascinating catalytic activities and extensively investigated as sensors and catalysts [12]. Pt hollow nanospheres have high surface area and therefore exhibit enhanced electrocatalytic performance for methanol electrooxidation [13]. Among various approaches to prepare metal hollow spheres, the method using silica spheres as template is a simple approach due to silica spheres have good monodispersity, wider size range, and are easy to be synthesized [14,15]. Despite the exceptional catalystic properties of metal hollow spheres, there is little information on the electrocatalytic properties of Ni hollow spheres. 2. Experimental The starting material is silica spheres, which were prepared using the Sto ber method [16]. In a typical procedure,

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4.7 ml of Si(OC2H5)4 (tetraethylorthosilicate, TEOS) was mixed with 16 ml water, 50 ml ethanol, and 9 ml of 28% ammonia. The mixture was stirred mildly for 3 h, then 0.2 ml of 3-aminopropyltrimethoxysilane (APTMS) was putted into the mixture. This mixture was continuously stirred for 12 h. This process provided aminemoieties coating on the surface of the silica spheres [17,18]. Small gold colloid nanoparticles (3.5 0.7 nm) were prepared by using the Jana method [19]. Excess 0.1 M NaBH4 solution was added into a solution (250 ml) containing 2.5 104 M HAuCl4 and 2.5 104 M trisodium citrate under stirring. Then APTMS-functionalized silica spheres with ethanol were added to the gold colloid solution for 12 h, which produced silica spheres with well-separated gold nanoparticles on the surface. These gold nanoparticles on the silica spheres were used as seeds for the growth of nickel shell. The precursor silica spheres covered with the gold nanoparticles were added to 5 103 M NiCl2 ethylene glycol solution under vigorous stirring, following addition of excess 0.9 M hydrazine. The pH value of the solution is adjusted to 8.5 by 0.1 M NaOH solution and the reaction lasted for 4 h at 60 C. During the reaction, the colour of the solution gradually evolved, which indicated the reduction of Ni2+ and the formation of a silicanickel coreshell

material. Finally, the silica core was dissolved in 2 M NaOH and the nickel shell was remained. Ni particles with an average particle size of 9 nm were synthesized at room temperature by chemical reduction using NaBH4. Excess 0.01 M NaBH4 solution was mixed with the NiCl2 solution under stirring. The resulted material was washed with deionized water and dried at 40 C in vacuum. The Ni hollow spheres and Ni particles with PTFE were cast onto a 0.50 cm2 carbon electrode and used as the work electrodes. The loadings of nickel and PTFE were 0.1 mg cm2 and 0.05 mg cm2. Electrochemical experiments were performed on a CHI 680b electrochemical work station (CH Instrument, Inc.). A standard three-electrode cell was used and controlled at 25 C using a water bath during the experiment. A platinum foil (3.0 cm2) and Hg/HgO (1.0 M KOH) were used as counter and reference electrode. X-ray diraction (XRD) was carried out on a D/MAX2200 diractometer. Transmission electron microscopy (TEM) was performed with a PHILIPS TECNAI-10 microscope. 3. Results and discussion Fig. 1a shows the typical TEM image of the gold nanoparticles immobilized on the outer surface of those silica

Fig. 1. (a) TEM image of the gold nanoparticles immobilized on the surface of silica spheres (the inset gure is the TEM image of silica spheres); (b) TEM image of silicanickel coreshell structure material; (c) TEM image of Ni hollow spheres (the inset gure is the EDAX of Ni hollow spheres); (d) TEM image of the Ni hollow spheres after heat treatment at 600 C for 1 h in H2.

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spheres in a well-dispersed way. Silica spheres with an average diameter of about 400 nm are shown in the inset gure in Fig. 1a. The silica spheres have smooth surface and spherical shape. Fig. 1b shows the typical TEM image of silicanickel coreshell structure material. The thickness of nickel shell is about 40 nm. The shell consists of needle-like nickel particles. Fig. 1c shows the typical TEM image of Ni hollow spheres. The inset gure in Fig. 1c is the energy dispersive X-ray analysis (EDXA) of Ni hollow spheres. The result shows that the weight content of Ni, Au, Si is 96.4%, 1.7%, 1.9%, showing that the SiO2 cores were removed after treatment in KOH solution. The needle-like particles are still on the surface of Ni hollow spheres. The TEM image of Ni hollow spheres with heat treatment in ow H2 at 600 C for 1 h is shown in Fig. 1d. The surface morphology of the nickel shell does not change signicantly and only the needle-like particles disappear. The hollow nickel spheres exhibit a good heat stability. Fig. 2 shows the XRD pattern of Ni hollow spheres with a typical face-centered-cubic (fcc) lattice structure. The strong diraction peaks at the Bragg angles of 44.5, 51.8 and 76.4 correspond to the (1 1 1), (2 0 0) and (2 2 0) facets of nickel crystal. The Ni(1 1 1) peak was used to calculate the particle size of nickel particles in the Ni hollow spheres according to the Sherrers equation. The average size of nickel particles in the Ni hollow spheres is 8.5 nm. Figs. 3 and 4 show the cyclic voltammograms of methanol and ethanol oxidation in 1.0 M KOH solution containing 1.0 M alcohol on Ni particles and Ni hollow spheres electrodes. The scan rate was 5 mV s1 in the potential range of 0.8 to 0.3 V. The cyclic voltammogram of Ni hollow spheres electrode in 1.0 M KOH with absence of alcohol is shown in inset gure of Fig. 3. A small hump at a potential value of about 0.6 V that corresponds to the oxidation of nickel according to the reaction [20] Ni 2OH ( ) NiOH2 2e 1

Fig. 3. Cyclic voltammograms of methanol oxidation on Ni particles and Ni hollow spheres (HS) electrodes with a nickel loading of 0.10 mg cm2 in 1.0 M KOH solution containing 1.0 M methanol with a sweep rate of 5 mV s1 (The inset gure is the cyclic voltammogram of Ni hollow spheres electrode in 1.0 M KOH with absence of alcohol).

Fig. 4. Cyclic voltammograms of ethanol oxidation on Ni particles and Ni hollow spheres (HS) electrodes with a nickel loading of 0.10 mg cm2 in 1.0 M KOH solution containing 1.0 M ethanol with a sweep rate of 5 mV s1.

The small anodic peak at a poertential value of about 0.15 V that corresponds to the oxidation Ni(OH)2 to NiOOH in accordance with the reaction [21]

NiOH2 OH ( ) NiOOH H2 O e

It is noted that the Ni(OH)2/NiOOH transformation occurred on Ni electrode reversibly. By comparing with the cyclic voltammogram in the absence of alcohol, an alcohol oxidation peak can be clearly observed in the cyclic voltammograms on Ni hollow spheres electrode in the presence of 1.0 M alcohol. It was suggested that alcohol is oxidized and NiOOH transformed to Ni(OH)2 [22]. The resolved alcohol would react with the electrode to form an intermediate, adsorbed alcohol with a chemical formula-RCHOHads, the following reactions [22 24] RCH2 OH NiOOH ! NiOOHRCH2 OHads NiOOHRCH2 OHads NiOOH ! NiOH2 NiOOHR COHads 3 4 5

Fig. 2. XRD pattern of Ni hollow spheres.

NiOOHR COHads NiOOH OH ! 2NiOH2 RCOO

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The peak current densities for methanol and ethanol oxidation on Ni hollow spheres are 25 and 17 mA cm2. The peak current densities for methanol and ethanol oxidation on Ni particles are 3.5 and 2.0 mA cm2. The current on Ni hollow spheres is much higher than that on Ni particles. The onset potential (Es) and peak potential (Ep) on Ni hollow spheres are more negative than that on Ni particles for methanol and ethanol electrooxidation. The onset potential on Ni hollow spheres for methanol and ethanol is more negative for about 350 mV compared to that on Ni particles. More than 350 mV reduction on the onset potential for anodic reaction is signicant for liquid fuel cell. The current peak on Ni hollow spheres begins to rise much more sharply at more negative potential, which will directly improve fuel cell eciency. The results show that Ni hollow spheres are highly active for methanol and ethanol oxidation at a very low nickel loading of 0.10 mg cm2. It is well known that the utilization eciency of catalysts is related to the morphology and distribution of the catalysts even the same composition because of the diusion of reactants and products during the reaction process [25]. Electrode surfaces are exquisitely sensitive to any redox active species that are able to diuse to the electrode/electrolyte interface during an electrochemical reaction [26,27]. The structure of hollow spheres forms larger three-phase interface and permits liquid alcohol to diuse into the catalysts layer easily, resulting in the reduction of liquid sealing eect and concentration polarization. They make liquid fuel diffuse into the inside and products diuse out of the catalyst layer much easier, therefore, the utilization eciency of catalysts gets higher. The mechanistic study is in progress. The in situ FTIR and other methods are being used to further study the reaction mechanism. 4. Conclusions In this paper, we used silica spheres as template and successfully synthesized Ni hollow spheres consisting of needle-like nickel particles by using Au nanoparticles seeding method. The Ni hollow spheres were used as electrocatalyst for methanol and ethanol oxidation in alkaline media. The study reveals that Ni hollow spheres are promising electrocatalysts for alcohol oxidation in alkaline media. The Ni hollow spheres in this paper show a high electrocatalytic activity for alcohol electrooxidation in alkaline media and may be of great potential in alcohol sensors and direct alcohol fuel cells.

Acknowledgement This work was nancially supported by the Science and Technology Project of Guangdong Province (2005A11001001) and Chinese Postdoctoral Prizing Funding (Xu Changwei, 20060390734). References
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