Elucidation of the selectivity of proton-dependent electrocatalytic CO2 reduction by fac-Re(bpy)(CO)3Cl.
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's, 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-CO2 intermediate anion precedes Brønsted-acid-catalyzed C-O 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.
Department of Mechanical and Aerospace Engineering and ‡Program in Applied and Computational Mathematics and ⊥Andlinger Center for Energy and the Environment, Princeton University , Princeton, New Jersey 08544-5263, United States.
John A
JA
Keith
Kyle A
KA
Grice
Clifford P
CP
Kubiak
Emily A
EA
Carter