Nanostructured Gold and Alloys for Fuel Cell Catalysis

Gold-based nanoparticles in the size range of a few nm have attracted increasing interests in catalysis, sensors and biomedical applications. The study of the unique catalytic properties of nanosized gold was inspired by the pioneering work of Haruta on the nanogold-catalyzed CO oxidation (1-4). There have been a number of excellent reports discussing both fundamental and application aspects of gold nanoparticles in catalysis (3-8). Our work reported herein is aimed at investigating the preparation and application of gold and its alloy nanoparticles for potential applications in fuel cell catalysis. Fuel cells operating by electrochemical oxidation of hydrogen or methanol fuels at the anode and reduction of oxygen at the cathode are attractive power sources due to their high conversion efficiencies, low pollution, lightweight and high power density. While methanol offers the advantage of easy storage and transportation in comparison with hydrogen fuel cell, its energy density (~2000 Wh/kg) and operating cell voltage (0.4 V) are much lower than the theoretical energy density (~6000 Wh/kg) and the thermodynamic potential (~1.2 V). The poor activity of the anode catalysts and inefficient activity or issue related to "methanol cross-over" at the cathode electrode are associated with the loss of about one-third of the available energy at the cathode and the other one-third at the anode. Extensive studies have been focused on Pt-group metals (Pt+Pd+Rh+Ru+Ir (PGM)) for both anode and cathode catalysts. A major problem is the poisoning of Pt by COlike intermediate species (9,10). Recently, oxide-supported gold nanoparticles in the <10 nm size range have emerged as one of the best catalysts for CO oxidation (1-3,11), and for water gas shift reaction in reforming stage using 5 nm Au on Fe2O3 (6). Gold and its alloy with other metals in the nanosize range present new alternatives (2,12). Whether the unique properties of gold nanoparticles can be exploited for addressing these problems is a focus area of our work. The ability to harness the large surface area-to-volume ratios and the unique surface sites of nanoparticles in <10 nm size range, especially in heterogeneous catalysis, constitutes a major driving force in fundamental research and practical applications of nanoparticle catalysts. It is this size range over which the metal particles undergo a transition from atomic to metallic properties. The understanding of factors controlling the morphological and surface reconstitution associated with such a size range is of fundamental importance to the ultimate exploration of nanostructured catalysts. We have been investigating the interfacial structures and properties of core-shell types of nanoparticles consisting of gold or alloy nanocrystal cores and organic monolayer shells that were prepared by twophase synthesis (13) and processing (14) protocols. Important attributes of such nanoparticles include controllable size monodispersity, processibility, and stability towards size- and composition-tunable catalysis (15-21). Some of these attributes were studied for understanding their electrocatalytic properties in the oxidation of methanol and reduction of oxygen, which are of fundamental interest to fuel cell technology.