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.
Highlights
The methanol (MeOH) oxidation reaction has attracted significant attention in the last decades, both from a fundamental and applied point of view [1,2,3,4,5]
It is generally accepted that methanol oxidation reaction occurs through a dual path mechanism, in which a path involves the formation of adsorbed CO, a poisoning intermediate, and a second path going through an active intermediate
The that methanol oxidation between the interfacial structure and the theresults resultsindicate indicate that methanol oxidation is only taking place when the surface is partially covered by adsorbed
Summary
The methanol (MeOH) oxidation reaction has attracted significant attention in the last decades, both from a fundamental and applied point of view [1,2,3,4,5]. Methanol is a small organic molecule and the knowledge acquired by studying its oxidation mechanism can be later transferred to more complex organic molecules. Its mechanism can serve as a model for the oxidation of more complex alcohols, such as ethanol or ethylene glycol. Methanol can be used as a fuel in fuel cells. The anodic over-potentials are significantly higher than those measured for the hydrogen oxidation reaction
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