Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO2 Reduction by fac-Re(bpy)(CO)3Cl

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• 作者：John A. Keith ; Kyle A. Grice ; Clifford P. Kubiak ; Emily A. Carter
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：October 23, 2013
• 年：2013
• 卷：135
• 期：42
• 页码：15823-15829
• 全文大小：390K
• 年卷期：v.135,no.42(October 23, 2013)
• ISSN：1520-5126

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 pK_a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.