Chemical Versatility of [FeFe]-Hydrogenase Models: Distinctive Activity of [μ-C6H4-1,2-(κ2-S)2][Fe2(CO)6] for Electrocatalytic CO2 Reduction

被引：30

作者：

Cheng, Minglun ^{[1
]}

Yu, Yang ^{[1
]}

Zhou, Xin ^{[2
]}

Luo, Yi ^{[1
]}

Wang, Mei ^{[1
]}

机构：

[1] Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China

[2] Dalian Univ, Coll Environm & Chem Engn, Dalian 116622, Peoples R China

来源：

ACS CATALYSIS | 2019年 / 9卷 / 01期

基金：

中国国家自然科学基金;

关键词：

carbon dioxide reduction; carbon monoxide; diiron complex; electrocatalysis; formic acid; hydrogenase model; CO2-TO-CO ELECTROCHEMICAL CONVERSION; BULKY BIPYRIDINE LIGANDS; CARBON-DIOXIDE; MOLECULAR CATALYSTS; NICKEL-COMPLEXES; FORMIC-ACID; PROTON; EFFICIENT; SITE; ACTIVATION;

D O I：

10.1021/acscatal.8b03921

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：

The [FeFe]-hydrogenase model, [(mu-bdt)Fe-2(CO)(6)] (1, bdt = benzene-1,2-dithiolato), displays distinctive activity from its analogous complex, [(mu-edt)Fe-2(CO)(6)] (2, edt = ethane-1,2-dithiolato), for electrochemical CO2 reduction in acetonitrile with methanol or water as proton source. The maximum turnover frequency of 195 s(-1) estimated for 1 is more than 4800 times higher than that of 2. The influence of reaction conditions on faradaic yield and product selectivity was investigated. Controlled potential electrolysis experiments of 1 under optimal conditions gave a good faradaic yield of 88%, with formic acid as major product (selectivity, approximate to 81%) together with a small amount of CO (selectivity approximate to 11%) and H-2 (selectivity approximate to 8%). Density functional theory calculations suggest a mechanism of bimetal synergistic catalysis for electrochemical CO2 reduction by 1.

引用

页码：768 / 774

页数：13

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