Mechanistic Study of Electrocatalytic Oxidation of Formic Acid at Platinum in Acidic Solution by Time-Resolved Surface-Enhanced Infrared Absorption Spectroscopy
Citations Over TimeTop 10% of 2006 papers
Abstract
Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account.
Related Papers
- → On the mechanism of the direct pathway for formic acid oxidation at a Pt(111) electrode(2013)101 cited
- → Adsorption of Formate and Its Role as Intermediate in Formic Acid Oxidation on Platinum Electrodes(2011)85 cited
- → Photooxidation of Formic Acid vs Formate and Ethanol vs Ethoxy on TiO2 and Effect of Adsorbed Water on the Rates of Formate and Formic Acid Photooxidation(2001)143 cited
- → CO2 hydrogenation to formic acid on Ni(110)(2012)100 cited
- → Formic acid–Formate blended solution: A new fuel system with high oxidation activity(2011)38 cited