On the oxidation of isopropanol on platinum single crystal electrodes. A detailed voltammetric and FTIR study

Abstract

Isopropanol oxidation is studied on platinum single crystals using electrochemical techniques and FTIR spectroscopy at different isopropanol concentrations. Isopropanol oxidation is found to be facilitated by the presence of adsorbed OH on the electrode surface, which reacts with an isopropanol molecule to yield the adsorbed alkoxide. Thus, when sulfuric acid is used as the supporting electrolyte instead of perchloric acid, oxidation currents diminish drastically since sulfate hinders OH adsorption. Kinetic measurements reveal that the chemical reaction between adsorbed OH and isopropanol is the rate-determining step in the mechanism. Voltammetric and FTIR experiments show that acetone is the major product of the reaction. On the Pt(111) surface, acetone is produced exclusively, and oxidation currents are controlled by diffusion since, on this electrode, acetone is not adsorbed and the adsorbed OH mobility is high. The adsorption of acetone-related species on the Pt(110) surface, which partially block the surface, leads to slightly lower currents. On the other hand, the Pt(100) electrode is the one showing significant rates for the C–C bond cleavage, yielding adsorbed CO and other species. Although this route is a minor path, the surface blockage by these species leads to a significant diminution of the currents.