Ethanol Electro-oxidation Reaction Selectivity on Platinum in Aqueous Media

Ethanol fuel cells require selective catalysts for complete oxidation of the fuel, which involves C–C bond cleavage. From experiments on well-defined surfaces and calculations, the mechanism controlling the ethanol electro-oxidation selectivity on platinum in aqueous media as a model system is elucidated. Adsorbed OH favors ethanol adsorption and conversion into adsorbed ethoxy, which favorably evolves to adsorbed COCH3. On Pt(111), adsorbed OH is also readily incorporated into adsorbed COCH3 to yield acetic acid. A higher barrier for this latter step on Pt(100) enables the COCH3 dehydrogenation to adsorbed COCH2, favoring C–C bond cleavage. As adsorbed OH plays an essential role as a reactant in this process, its adsorption properties have a decisive impact on this reaction. Furthermore, the adsorbed OH diffusion rate on the surface, which depends on the adsorbate/media/surface interaction at the interface, modulates the availability of this key reactant. These results highlight that the search for selective electrocatalysts requires holistic consideration of reactants, adsorbates, media, and substrate.