Relationship between oxide identity and electrocatalytic activity of platinum for ethanol electrooxidation in...

Water and its dissociated species at the solid‒liquid interface play critical roles in catalytic science; e.g., functions of oxygen species from water dissociation are gradually being recognized. Herein, the relationship between oxide identity (PtOH_ads, PtO_ads, and PtO₂) and electrocatalytic activity of platinum for ethanol electrooxidation was obtained in perchlorate acidic solution over a wide potential range with an upper potential of 1.5 V (reversible hydrogen electrode, RHE). PtOH_ads and α-PtO₂, rather than PtO_ads, act as catalytic centers promoting ethanol electrooxidation. This relationship was corroborated on Pt(111), Pt(110), and Pt(100) electrodes, respectively. A reaction mechanism of ethanol electrooxidation was developed with DFT calculations, in which platinum oxides-mediated dehydrogenation and hydrated reaction intermediate, geminal diol, can perfectly explain experimental results, including pH dependence of product selectivity and more active α-PtO₂ than PtOH_ads. This work can be generalized to the oxidation of other substances on other metal/alloy electrodes in energy conversion and electrochemical syntheses.