Origin of the Drastic Current Decay during Potentiostatic Alkaline Methanol Oxidation.

The current production from the alkaline methanol electro-oxidation reaction does not reach a steady state on a smooth platinum catalyst under potentiostatic conditions. We investigated two possible explanations for this phenomenon: changes on the catalyst surface and changes in the solution near the electrode. In situ Fourier transform infrared spectroscopy experiments were conducted to evaluate the adsorbed species on the catalyst surface and a simulation model was set up to describe the changes of concentrations inside the solution. Linear- and bridge-bonded carbon monoxide are the only organic compounds which can be detected by in situ spectroscopy at fixed potentials, but their amount does not increase over time. The simulation shows that the consumption of hydroxide ions and production of carbonaceous species during alkaline oxidation causes a local pH shift near the catalyst surface. Assuming a one-electron transfer as the limiting step, this pH shift was found to contribute to the observed current loss at a potential of 0.77 V.