Electronic Structures of Pt−Co and Pt−Ru Alloys for CO-Tolerant Anode Catalysts in Polymer Electrolyte Fuel Cells Studied by EC−XPS

Abstract

CO tolerance at pure Pt, Pt−Co, and Pt−Ru alloys was investigated by X-ray photoelectron spectroscopy combined with an electrochemical cell (EC−XPS) in order to discover a hint for designing higher performance anode catalysts. After the electrochemical stabilization and/or CO adsorption, these electrodes were immediately transferred to the XPS chamber without exposure to air to avoid contamination of the surfaces. It was revealed that alloying with Co or Ru modified the electronic structures of Pt atoms, resulting in a positive core level (CL) shift of Pt 4f_7/2 which could weaken the Pt−CO interaction. For the Pt−Co alloy electrode, the Pt 4f_7/2 CL shift remained after the electrochemical stabilization despite Co dissolution and formation of a Pt skin layer. Changes in surface core level shifts (ΔSCLSs) induced by CO adsorption were evaluated and related to the CO adsorption energy. The values of ΔSCLS at these alloys were smaller than that of pure Pt, indicating that Ru and Co are effective elements to weaken the bond strength of Pt−CO.