Bimetallic Nanoparticles of PtCu and PtNi; Synthesis and CO Oxidation Catalysis
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1217-Y08-03
Bimetallic Nanoparticles of PtCu and PtNi; Synthesis and CO Oxidation Catalysis
Takao A. Yamamoto, Takashi Nakagawa, Satoshi Seino and Hiroaki Nitani∗ Grad. Sch. Eng. Osaka University, Yamadaoka 2-1, Suita, Osaka, 565-0871, Japan.
ABSTRACT Bimetallic nanoparticles of PtCu and PtNi supported on iron oxide particles were synthesized by a new method employing a 4.8-MeV electron beam as a trigger for reduction of their aqueous ions, and their CO oxidation catalysis was evaluated to find activities enhanced by the alloying. Sample materials of PtCu (PtNi) bimetallic grains supported on γ-Fe2O3 particles were synthesized by irradiating with the electron beam a glass vial containing precursors in an aqueous solution. The vial contains aqueous ions of platinum and copper (nickel) and γ-Fe2O3 particles of average size of 30 nm. The irradiation induces water radiolysis generating reducing species, such as hydrated electrons, and metallic nanograins are formed and stabilized on the support material. The irradiation was finished in several seconds without using any organic solvent and any surfactant. The average grain sizes observed with a TEM were around 3 nm in diameter. XRD patterns of PtCu samples exhibited the FCC structure with peak shifts obeying the Vegard’s law at low Cu concentrations. X-ray absorption spectra measured at edges of the constituent elements indicated that Pt is in the metallic state and coordinates certainly with Cu or Ni. Catalytic activity of CO oxidation of the material was evaluated by measuring residual CO contents in air in contact with the sample material by using a gas-chromatograph. The activities of the PtCu and PtNi samples were higher than that of monolithic Pt on γ-Fe2O3. The correlation between the atomic structure in these nanograins and their activities was investigated, which indicated that the random alloy enhances the activity. These bimetallic nanoparticles are expected as catalysts for preferential oxidation of CO in hydrogen gas fed to fuel cells. INTRODUCTION Fuel cell is the key technology of near future energy system, and the major problem confronting its popularization is the high cost of Pt and other noble metals containing in catalysts. Enhanced catalysis with less Pt contents is required and its development is an important task of scientists and engineers. One route to such advanced catalysis is to enhance activity by an appropriate atomic structure of Pt and additional cheaper element playing role not only of a diluent but also an enhancer [1]. For instance, methanol oxidation occurring on anode is enhanced by addition of Ru to the Pt, which is explained by “bi-functional mechanism” as follows [2]. Pt poisoned by CO molecule is liberated by OH adsorbed by Ru adjacent to the Pt to produce CO2. Such Pt-Ru atomic pairs on the catalyst surface are the origin of this ∗
Present affiliation: Inst. Mater. Struct. Sci., KEK, Oho 1-1, Tsukuba, Ibaraki, 305-0801, Japan.
enhancement. However, even when an alloy is the equilibrium phase in the bulk material, it is ofte
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