Effect of Mass Transport on the Electrochemical Oxidation of Alcohols Over Electrodeposited Film and Carbon-Supported Pt Electrodes.

Electrochemical oxidation of four different alcohol molecules (methanol, ethanol, -butanol and 2-butanol) at electrodeposited Pt film and carbon-supported Pt catalyst film electrodes, as well as the effect of mass transport on the oxidation reaction, has been studied systematically using the rotating disk electrode (RDE) technique. It was shown that oxidation current decreased with an increase in the rotation rate (ω) for all alcohols studied over electrodeposited Pt film electrodes. In contrast, the oxidation current was found to increase with an increase in the ω for Pt/C in ethanol and -butanol-containing solutions. The decrease was found to be nearly reversible for ethanol and -butanol at the electrodeposited Pt film electrode ruling out the possibility of intermediate CO poisoning being the sole cause of the decrease and was attributed to the formation of soluble intermediate species which diffuse away from the electrode at higher ω. In contrast, an increase in the current with an increase in ω for the carbon supported catalyst may suggest that the increase in residence time of the soluble species within the catalyst layer, results in further oxidation of these species. Furthermore, the reversibility of the peak current on decreasing the ω could indicate that the surface state has not significantly changed due to the sluggish reaction kinetics of ethanol and -butanol.