Kinetics and mechanism of interaction between methanol and adsorbed oxygen on a smooth polycrystalline platinum electrode: Transients of the open-circuit potential

Abstract

The method of transients of the open-circuit potential, combined with cathodic potentiodynamic pulses, is used for studying the methanol interaction with preliminarily adsorbed oxygen (Oads) in 0.5 M H2SO4. It is established that, for the larger part of the time period required for a full reduction of a monolayer of Oads in solutions of methanol on polycrystalline platinum, the process occurs at large coverages of the surface by Oads (ϑO). In the region of medium coverages, transients of the open-circuit potential are accurately described by the equation that corresponds to the mechanism of “conjugated reactions.” The mechanism of the methanol interaction with Oads happens to be close to that for formic acid, which is explained by a dissociative character of these HCO compounds. Kinetic parameters characterizing the methanol reaction with Oads in the region of large and medium coverages are determined and analyzed.