Effects of the Interfacial Structure on the Methanol Oxidation on Platinum Single Crystal Electrodes

Abstract

Methanol oxidation has been studied on low index platinum single crystal electrodes using methanol solutions with different pH (1–5) in the absence of specific adsorption. The goal is to determine the role of the interfacial structure in the reaction. The comparison between the voltammetric profiles obtained in the presence and absence of methanol indicates that methanol oxidation is only taking place when the surface is partially covered by adsorbed OH. Thus, on the Pt(111) electrode, the onset for the direct oxidation of methanol and the adsorption of OH coincide. In this case, the adsorbed OH species are not a mere spectator, because the obtained results for the reaction order for methanol and the proton concentrations indicate that OH adsorbed species are involved in the reaction mechanism. On the other hand, the dehydrogenation step to yield adsorbed CO on the Pt(100) surface coincides with the onset of OH adsorption on this electrode. It is proposed that adsorbed OH collaborates in the dehydrogenation step during methanol oxidation, facilitating either the adsorption of the methanol in the right configuration or the cleavage of the C—H bond.