Electrocatalytic Oxidation of Small Molecule Alcohols over Pt, Pd, and Au Catalysts: The Effect of Alcohol’s Hydrogen Bond Donation Ability and Molecular Structure Properties

The direct alcohol fuel cell is a kind of power generation device that directly converts the chemical energy of small molecule alcohols into electric energy. In this paper, the electro-oxidation behaviors of some typical alcohols (methanol, ethanol, ethylene glycol, n-propanol, 2-propanol, and glycerol) over Pt, Pd, and Au electrodes were investigated in acidic, neutral, and alkaline media, respectively. By analyzing the activity information from a cyclic voltammetry (CV) method and some dynamic tests, several regularities were revealed in those electro-oxidation behaviors. Firstly, alkaline media is the best for the electro-oxidation of all these alcohols over Pt, Pd, and Au catalysts. Secondly, the hydrogen bond donation abilities (HBD) of different alcohols were found have a great relationship with the catalytic performance. In alkaline media, on Pt electrodes, the solute HBD is positively correlated with the ease of electrooxidation within the scope of this experiment. Contrarily, it is negatively correlated on Pd and Au electrodes. Additionally, for Pt catalysts in acidic and neutral media, the relationship becomes negative again as the HBD increases. Finally, the alcohol’s molecular structure properties were found to have a remarkably influence on the activity of different catalysts. Over the Pt electrode in alkaline media, the activation energy of methanol oxidation is 44.1 KJ/mol, and is obviously lower than the oxidation of other alcohols. Under similar conditions, the lowest activation energy was measured in the oxidation of n-propanol (14.4 KJ/mol) over the Pd electrode, and in the oxidation of glycerol (42.2 KJ/mol) over the Au electrode. Totally, among all these electrodes, Pt electrodes showed the best activities on the oxidation of C1 alcohol, Pd electrodes were more active on the oxidation of C2-3 monobasic alcohols, and Au electrodes were more active on the oxidation of polybasic alcohols.