Highly Active Manganese-Based CO2 Reduction Catalysts with Bulky NHC Ligands: A Mechanistic Study

Yang, Yong1; Zhang, Zhenyu1; Chang, Xiaoyong1; Zhang, Ya-Qiong4; Liao, Rong-Zhen4; Duan, Lele1,2,3

2020-07-20

10.1021/acs.inorgchem.0c01364

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

Because of the strong sigma-donor and weak pi-acceptor of the N-heterocyclic carbene (NHC), Mn-NHC complexes were found to be active for the reduction of CO2 to CO with high activity. However, some NHC-based manganese complexes showed low catalytic activity and required very negative potentials. We report herein that complex fac-[Mn-I(bis-(NHC)-N-mes)(CO)(3)B]r [1; bis-(NHC)-N-Mes = 3,3-bis(2,4,6-trimethylphenyl)-(1,1'-diimidazolin-2,2'-diylidene)methane] could catalyze the electrochemical reduction of CO2 to CO with high activity (TOFmax = 3180 +/- 6 s(-1)) at a less negative potential. Due to the introduction of the bulky Mes groups, a one-electron-reduced intermediate {[Mn-0(bis-(NHC)-N-Mes)(CO)(3)](0) (2(center dot))} was isolated as a packed "dimer" and crystallographically characterized. Stopped-flow Fourier-transform infrared spectroscopy was used to prove the direct reaction between doubly reduced intermediate fac-[Mn(bis-(NHC)-N-Mes)(CO)(3)](- )and CO2 ; the tetracarbonyl Mn complex [Mn+(bis-(NHC)-N-Mes)(CO)(4)](+) ([2-CO](+)) was captured, and its further reduction proposed as the rate-limiting step.

SCI ; EI

英语

NI论文

第一 ; 通讯

Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; National Natural Science Foundation of China[21771098] ; Science and Technology Innovation Commission of Shenzhen Municipality[JCYJ20170817111548026] ; Shenzhen Clean Energy Research Institute[CERI-KY-2019-003] ; Guangdong Provincial Key Laboratory of Energy Materials for Electric Power[2018B030322001]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000552287100077

AMER CHEMICAL SOC

20202908939332

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol SUSTech, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol SUSTech, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol SUSTech, Guangdong Prov Key Lab Energy Mat Elect Power, Shenzhen 518055, Peoples R China
4.Huazhong Univ Sci & Technol, Sch Chem & Chem Engn, Key Lab Mat Chem Energy Convers & Storage, Minist Educ, Wuhan 430074, Peoples R China

Yang, Yong,Zhang, Zhenyu,Chang, Xiaoyong,et al. Highly Active Manganese-Based CO2 Reduction Catalysts with Bulky NHC Ligands: A Mechanistic Study[J]. INORGANIC CHEMISTRY,2020,59(14):10234-10242.

Yang, Yong,Zhang, Zhenyu,Chang, Xiaoyong,Zhang, Ya-Qiong,Liao, Rong-Zhen,&Duan, Lele.(2020).Highly Active Manganese-Based CO2 Reduction Catalysts with Bulky NHC Ligands: A Mechanistic Study.INORGANIC CHEMISTRY,59(14),10234-10242.

Yang, Yong,et al."Highly Active Manganese-Based CO2 Reduction Catalysts with Bulky NHC Ligands: A Mechanistic Study".INORGANIC CHEMISTRY 59.14(2020):10234-10242.