NEW PERSPECTIVES IN ELECTROCHEMICAL PROCESSES ON SINGLE-CRYSTAL SURFACES FROM REAL-TIME FTIR SPECTROSCOPY

Some recent applications of surface infrared spectroscopy to the mechanistic examination of electrocatalytic processes at monocrystalline metalaqueous solution interfaces are outlined, with emphasis on the use of real-time FTIR combined with simultaneous or parallel electrochemical measurements. Carbon monoxide electrooxidation on low-index platinum and rhodium surfaces is considered in relation to the behavior at monocrystalline gold. The central role of island formation during electrooxidation of CO adlayers on the former surfaces is implicated directly by the infrared data. The large effects of gold crystallographic orientation on the CO electrooxidation rates are discussed in terms of reactant adsorptive and surface stereochemical factors. Other illustrative examples considered are the examination of dissociative chemisorption mechanisms of methanol and ethanol on Rh(100), and the catalytic effect of bismuth adatoms on formic acid electrooxidation at Pt(100).