Carbon-supported bimetallic Pt m Ni n electrocatalysts with different Pt/Ni atomic ratios were synthesized through a modified polyol process. The as-prepared electrocatalysts were characterized by X-ray diffraction, transmission electron microscopy, voltammetry techniques, and single-cell tests. It was revealed that the Pt m Ni n bimetallic nanoparticles were uniformly distributed on carbon supports with average diameters of about 3 nm. Pt and Ni were partially alloyed, indicated by the decreased Pt lattice constants compared with that of pure Pt. The results of the electrochemical measurements showed that the Pt m Ni n /C catalysts, compared with the Pt/C, have superior specific activity toward the methanol electrooxidation reaction (MOR) in alkaline media as well as a higher power density in a direct methanol fuel cell test with the Pt 3 Ni 1 /C as the anode catalyst. Density functional theory studies further revealed that the electronic structure of Pt was modified by Ni due to the charge transfer from Ni to Pt atoms in Pt m Ni n clusters, leading to a weakened CO adsorption on Pt m Ni n binary clusters than on Pt itself. This provides an explanation for the enhanced MOR activity of the Pt m Ni n /C catalysts.
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