文摘
A complete mechanism for the proton-dependent electrocatalytic reduction of CO2 to CO by fac-Re(bpy)(CO)3Cl that is consistent with experimental observations has been developed using first principles quantum chemistry. Calculated one-electron reduction potentials, nonaqueous pKa鈥檚, reaction free energies, and reaction barrier heights provide deep insight into the complex mechanism for CO2 reduction as well as the origin of selectivity for this catalyst. Protonation and then reduction of a metastable Re鈥揅O2 intermediate anion precedes Br酶nsted-acid-catalyzed C鈥揙 cleavage and then rapid release of CO at negative applied potentials. Conceptually understanding the mechanism of this rapid catalytic process provides a useful blueprint for future work in artificial photosynthesis.