Applications of real-time infrared spectroscopy to electrocatalysis at bimetallic surfaces: I. Electrooxidation of formic acid and methanol on bismuth-modified Pt(111) and Pt(100)

摘要: The influence of predosed bismuth upon the electro-oxidation formic acid and methanol to CO2 on Pt(111) (100) in 0.1M HClO4 is examined by means voltammetry combined with real-time infrared spectroscopy. substantial (up 30–40-fold) enhancement rates observed presence Pt(100) are be due primarily attenuation degree CO poison formation as discerned from FTIR. adsorbed formation, which reaches near-saturation coverages absence bismuth, essentially eliminated for above ca. 0.2. production terminal triggered onset oxidation, suggesting that it forms a reactive intermediate rather than itself. bismuth-induced electrocatalysis oxidation apparently also arises similar manner, although major this case not CO. These electrocatalytic influences consistent an “ensemble effect”, whereby suppressed markedly greater precursor. In contrast, especially diminished bismuth. addition, formed during correlate directly variation reaction altering either reactant concentration or coverage. results suggest can act under these conditions. A consistency dissociation yield electrochemical versus UHV surface environments.