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

被引：245

作者：

Keith, John A. ^{[1
]}

Grice, Kyle A. ^{[4
]}

Kubiak, Clifford P. ^{[4
]}

Carter, Emily A. ^{[1
,2
,3
]}

机构：

[1] Princeton Univ, Dept Mech & Aerosp Engn, Princeton, NJ 08544 USA

[2] Princeton Univ, Program Appl & Computat Math, Princeton, NJ 08544 USA

[3] Princeton Univ, Andlinger Ctr Energy & Environm, Princeton, NJ 08544 USA

[4] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 42期

关键词：

CARBON-DIOXIDE; ELECTROCHEMICAL REDUCTION; MOLECULAR CALCULATIONS; HYDROGEN ELECTRODE; BASIS-SETS; POTENTIALS; PYRIDINIUM; METHANOL; RHENIUM; COMPLEXES;

D O I：

10.1021/ja406456g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A complete mechanism for the proton-dependent electrocatalytic reduction of CO2 to CO by fac-Re(bpy)(CO)(3)Cl that is consistent with experimental observations has been developed using first principles quantum chemistry. Calculated one-electron reduction potentials, nonaqueous pK(a)'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 Bronsted-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.

引用

页码：15823 / 15829

页数：7

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