N-Heterocylic Carbene-Based Mn Electrocatalyst for Two-Electron CO2 Reduction over Proton Reduction

被引：37

作者：

Rawat, Kuber Singh ^{[1
]}

Mahata, Arup ^{[1
]}

Choudhuri, Indrani ^{[1
]}

Pathak, Biswarup ^{[1
,2
]}

机构：

[1] Indian Inst Technol IIT Indore, Sch Basic Sci, Discipline Chem, Indore 452020, Madhya Pradesh, India

[2] Indian Inst Technol IIT Indore, Ctr Mat Sci & Engn, Indore 452020, Madhya Pradesh, India

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2016年 / 120卷 / 16期

关键词：

DENSITY-FUNCTIONAL THERMOCHEMISTRY; WEAK BRONSTED ACIDS; CARBON-DIOXIDE; ELECTROCHEMICAL REDUCTION; MOLECULAR CALCULATIONS; THEORETICAL INSIGHTS; METHANOL SYNTHESIS; REDOX POTENTIALS; METAL-COMPLEX; ONE-ELECTRON;

D O I：

10.1021/acs.jpcc.6b02209

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A bifunctional, chelating N-heterocyclic carbene-pyridine (NHC-pyridine) containing Mn(I) complex [MnBr(NHC-pyridine) (CO)(3)] displays a strong selectivity for CO2 reduction over proton reduction. Interestingly, the two-electron reduction of this complex occurs at a single potential, as opposed to MnBr(bpy)(CO)(3), which is reduced by two electrons in two separate one-electron reductions. Here, the Gibbs free energy barriers, reduction potentials, rate constants, and pK(a) values are predicted with theory to understand the one-vs two-electron reduction mechanism. The effects of weak and strong Bronsted acids [HCl, TFE (2,2,2-trifluoroethanol), PhOH, CH3OH, and H2O] are studied to gauge the preference for CO2 vs proton reduction; water is found to be an ideal proton donor that allows for strong CO2 selectivity.

引用

页码：8821 / 8831

页数：11

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