Anodic oxidation of methyl formate and its relationship to the reactions of methanol and formic acid

Experiments have been performed to examine the anodic oxidation of methyl formate in sulphuric acid using a platinum–ruthenium electrocatalyst, and to relate the process to the anodic oxidation of methanol and formic acid. Formic acid is more readily anodically oxidised than methanol, with up to five times the rate being observed, dependent on potential and temperature. The rate of reaction of methyl formate is comparable with that of formic acid. It is reasoned that the oxidation of the ester occurs most rapidly on the formate component, with methanol being generated by hydrolysis. The initial activation overpotential barrier required to oxidise these materials at a significant rate is common to all three fuels.