Increased Electrochemical Oxidation Rate of Alcohols in Alkaline Media on Palladium Surfaces Electrochemically Modified by Antimony, Lead, and Tin

Abstract

Several adatoms (M=Sb, Sn, or Pb) were added to Pd nanoparticles and examined for the electrochemical oxidation of ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, and glycerol. We observed a significant increase in oxidation rate on Pd-M for each of the adatoms in each of the fuels. For example, the oxidation rate of ethanol was 1.5 times greater on Pd-Pb and Pd-Sn as compared with the oxidation rate on Pd after 10minutes of oxidation. However, even more notable is the behavior observed by the polyhydric alcohols that exhibit sluggish reaction kinetics even in alkaline media. For example, the oxidation rate of propylene glycol on Pd-Pb was observed to be 21 times greater than the oxidation rate on Pd after 10minutes, and it was still 7.1 times greater after 12hours. These results show particular promise for the potential of efficiently oxidizing bulkier and higher energy density alcohols in the alkaline direct liquid fuel cell. All three bimetallic surfaces induced an increase in oxidation rate with all alcohols as compared to the monometallic Pd. Based on analysis of our results, we attribute a significant amount of the increase in oxidation rate to the bifunctional effect and suggest a lesser role is played by the electronic effect.