We elucidated theoretically an electrooxidation reaction mechanism of ethanol on a metal-organic framework (MOF) electrocatalyst, (HOC 2H4)2dtoaCu (H2dtoa = dithiooxamide), by using the density functional theory method. The indirect proton transfer from ethanol to the MOF via the HOC2H4 group is revealed to be a key mechanism controlling the reactivity of ethanol oxidation on MOF. We have also studied the ethanol oxidation reaction pathways on a series of R2dtoaCu (R = HOC3H6, C 2H5, C3H7, CH3, and H). Three dominant factors in the electrooxidation activity of R2dtoaCu were identified: (1) adsorptive interaction with the MOF; (2) strain in the backbone structure that enhances its activity as a proton acceptor; and (3) a proton-transfer pathway from ethanol to R2dtoaCu. These theoretical identifications are confirmed with the experimental results for ethanol sorption isotherms and the activity of the ethanol electrooxidation reaction measured for R2dtoaCu (R = HOC3H6 and C 2H5). We are the first to demonstrate the oxidation reaction mechanism of the MOF electrocatalyst for ethanol with theoretical study.
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films