GOLD BASED CORE-SHELL NANOPARTICLES AS FUEL CELL CATALYTS

Mathew M. Maye, Jin Luo, Sandy Chen, Wai-Ben Chan, H. Richard Nasland, Chuan-Jian Zhong* Department of Chemistry, State University of New York at Binghamton, Binghamton, NY 13902. * cjzhong@binghamton.edu

and the formation of oxides less than the electrochemical activation (8). Interestingly, the catalytic activity upon activation was also found to be dependant on the nature of the molecular-wire agent used to assemble the nanoparticle catalysts. We are systematically investigating several parameters that can be controlled (i.e., alloy composition, size, calcination, loading, etc.), and develop an in-depth delineation of these parameters with the catalytic activities. The results should provide important insights for the exploration of gold nanoparticles in practical fuel cell catalysis.

The ability to control the size of gold materials in the range of a few nanometers is important for the exploration of the unique catalytic properties of gold [1,2]. This presentation describes an investigation of the preparation of gold and gold alloy nanoparticles as electrocatalysts in several reactions including methanol oxidation, carbon monoxide oxidation and oxygen reduction. The goal is to explore the potential use of such nanoparticles as fuel cell catalysts. Core-shell type gold nanoparticles of 1-10 nm core size with organic monolayer encapsulation are studied for the preparation of catalysts towards the electroreduction of oxygen and the electrooxidation of carbon monoxide and methanol. The low catalytic activity, poisoning or instability of many existing platinum based metal catalysts are some of the current challenges to the development of fuel cell catalyst technology. It is thus important to develop a fundamental understanding of the correlation between the size, shape, and interparticle spatial properties and the catalytic activities. We choose to explore monolayer-capped nanoparticles because highly monodispersed nanoparticles with 2-5 nm core sizes ( 0.30.7 nm) can be easily prepared by a combination of two-phase synthesis and thermal processing protocols [3,4]. We have studied the assembly of these core-shell nanoparticles on high surface area carbon materials to evaluate their catalytic properties. The catalytic activities of the nanostructured catalysts have been studied in both acidic and alkaline electrolytes. Different alloy compositions of gold with other transition metals were varied using synthetic and processing protocols. The loading of catalysts on metal oxides (e.g., TiO2) and carbon supporting materials has been systematically investigated. The catalytic activation and fuel cell performance have also been evaluated. Both electrochemical and thermal approaches have been used to activate the catalysts. For the electrochemically-activated gold nanoparticles assembled on glassy carbon electrodes, which involved the application of a polarization potential to ~+800 mV, an anodic wave was observed for the oxidation of methanol in alkaline electrolytes, which closely matched the potential for Au oxide formation (Figure 1) (5,6). This observation, along with the anodic current exhibiting a linear increase with methanol concentration, whereas the cathodic wave decreased with methanol concentration, is again supportive of an electrocatalytic mediation mechanism. In electrochemical quartz crystal nanobalance measurements, a mass wave was detected corresponding to this current wave, implying an initial product release followed by formation of surface oxygenated species. The surface of the activated nanocrystals was examined using x-ray photoelectron spectroscopy (XPS) (7), which indicated the effective removal of the capping agents and the formation of surface oxides on gold nanocrystals. In comparison with the electrochemically-activated catalysts, similar results have been observed for thermally activated gold catalysts. XPS analysis of the catalysts has revealed a complete removal of the shell components

Figure 1. Current and mass responses for the electrocatalytic oxidation of methanol at activated NDT-linked Au2-nm on GC electrode in 0.5 M KOH with 3.0 M methanol (solid line) and without (dotted line). (Electrode geometric area: 0.2 cm2; scan rate: 50 mV/s). Recently, we have been investigating the catalytic properties of these nanomaterials in several fuel cell reactions. Latest results from electrochemical measurements of catalytic activities, along with XPS, XRD, HRTEM, and FTIR characterizations of structures and morphologies, have revealed that gold-based alloy nanoparticles (1-5 nm) are electrocatalytically active towards MeOH oxidation, CO oxidation, and O2 reduction. Using carbon black and TiO2 as supporting materials, these nanoparticles have shown high catalytic activity in both acidic and alkaline electrolytes under room temperature. Implications of the results to further refinement of the catalyst preparation in terms of composition and size will be discussed. References:
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Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 756