Electrocatalytic hydrogen evolution from water at low overpotentials with cobalt complexes supported by redox-active bipyridyl-NHC donors

作     者：Lizhu Chen Xiaojun Su Jonah W.Jurss Lizhu Chen;Xiaojun Su;Jonah W.Jurss

作者机构：Department of Chemistry and BiochemistryUniversity of MississippiUniversityMS 38677USA 

出 版 物：《Chinese Journal of Catalysis》 (催化学报（英文）)

年 卷 期：2022年第43卷第12期

页      面：3187-3194页

核心收录：

学科分类：081704[工学-应用化学] 081705[工学-工业催化] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：国家科学基金(CHE-1848478) 

主　　题：Redox-active bipyridyl N-heterocyclic carbene donors Cobalt complex Electrocatalysis Water splitting Hydrogen evolution 

摘      要：Three cobalt complexes bearing tunable,redox-active bipyridyl N-heterocyclic carbene(NHC)-based ligands have been studied for electrocatalytic hydrogen evolution from aqueous *** effect of structural modifications to the ligand framework is investigated across the catalyst series,which includes a non-macrocyclic derivative(1-Co)and 16-(2-Co)and 15-(3-Co)membered macrocycles.A structure-activity relationship is demonstrated,in which the macrocyclic complexes have greater activity compared to their non-macrocyclic counterpart with the most rigid catalyst,supported by the 15-membered macrocycle,performing best ***,3-Co catalyzes H2 evolution from aqueous pH 4 acetate buffer with a Faradaic efficiency of 97%at a low overpotential of 330 *** studies are consistent with formation of a cobalt-hydride species that is subsequently protonated to evolve H2 via a heterolytic pathway.