An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO2-to-CO reduction at low overpotential

Yang，Yong1; Ertem，Mehmed Z.2; Duan，Lele1

2021-04-07

10.1039/d0sc05679k

Chemical Science   影响因子和分区

2041-6520

2041-6539

The [fac-Mn(bpy)(CO)Br] complex is capable of catalyzing the electrochemical reduction of COto CO with high selectivity, moderate activity and large overpotential. Several attempts have been made to lower the overpotential and to enhance the catalytic activity of this complex by manipulating the second-coordination sphere of manganese and using relatively stronger acids to promote theprotonation-firstpathway. We report herein that the complex [fac-Mn(bpy-CONHMe)(CO)(MeCN)]([1-MeCN]; bpy-CONHMe =N-methyl-(2,2′-bipyridine)-6-carboxamide) as a pre-catalyst could catalyze the electrochemical reduction of COto CO with low overpotential and high activity and selectivity. Combined experimental and computational studies reveal that the amide NH group not only decreases the overpotential of the Mn catalyst by promoting thedimerandprotonation-firstpathways in the presence of HO but also enhances the COelectroreduction activity by facilitating C-OH bond cleavage, making [1-MeCN]an efficient COreduction pre-catalyst at low overpotential.

SCI ; EI

英语

NI论文

第一

Chemistry

Chemistry, Multidisciplinary

WOS:000637925000012

ROYAL SOC CHEMISTRY

20211510207265

Amides ; Catalyst activity ; Coordination reactions ; Electrolytic reduction

Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1

2-s2.0-85103912982

Scopus

1.Department of Chemistry,Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Energy Materials for Electric Power,Southern University of Science and Technology,Shenzhen,518055,China
2.Chemistry Division,Energy & Photon Sciences,Brookhaven National Laboratory,Upton,11973-5000,United States

Yang，Yong,Ertem，Mehmed Z.,Duan，Lele. An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO2-to-CO reduction at low overpotential[J]. Chemical Science,2021,12(13):4779-4788.

Yang，Yong,Ertem，Mehmed Z.,&Duan，Lele.(2021).An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO2-to-CO reduction at low overpotential.Chemical Science,12(13),4779-4788.

Yang，Yong,et al."An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO2-to-CO reduction at low overpotential".Chemical Science 12.13(2021):4779-4788.