DFT-based study on the optimal CH3OH decomposition pathways in aqueous-phase: Homolysis versus heterolysis

Our present study indicates that solvent effect can alter CH3OH decomposition pathways and identifies for the first time the presence of a dual reaction mechanism for CH3OH heterolytic decomposition that proceeds through formation of CH2OH and CH3O intermediates, whereas only initial C-H bond dissociation mechanism is identified in homolytic pathways. Furthermore, the homolytic and heterolytic pathways may be able to occur simultaneously on Pt(1 1 1) based on our DFT calculations. The present study can provide a new insight into modeling dehydrogenation reactions in aqueous-phase and help to achieve the ultimate goal of the design of Pt-based alloy electrocatalysts for CH3OH decomposition.