Activating and deactivating mass transport effects in methanol and formic acid oxidation on platinum electrodes

Transient increases in rotation rate at an RDE increase the methanol oxidation current, even though in slower experiments the current decreases with increasing rotation rate as usually reported. Methanol oxidation on smooth polycrystalline platinum rotating disk electrodes in sulfuric acid electrolyte was studied by RDE voltammetry and hydrodynamic impedance spectroscopy combined with cyclic voltammetry. A positive low-frequency real part in the hydrodynamic admittance spectra for the main oxidation peak was used to predict that a transient increase in rotation rate would increase the current, as was observed. In contrast, slow scan rate voltammograms showed a decrease in current with increasing rotation rate. The transient current increase was explained by enhanced production of soluble intermediates, while increased production of adsorbed CO poisoning explained the slower inhibition. Comparative experiments for formic acid oxidation showed increasing current with rotation rate in both hydrodynamic admittance spectra and slow-scan voltammograms.