In a carbon dioxide reduction reaction(CO_(2)RR),metal carbonyl intermediate not only serves as the 2e-/2H+reduction product,but it also contributes to CO release for catalyst regeneration.In the past decade,a large n...In a carbon dioxide reduction reaction(CO_(2)RR),metal carbonyl intermediate not only serves as the 2e-/2H+reduction product,but it also contributes to CO release for catalyst regeneration.In the past decade,a large number of studies have demonstrated that a catalyst binds,activates,and achieves electron transfer to CO_(2).However,the formation of metal carbonyl intermediate and release of CO during the CO_(2)RR process have not received the same level of attention.Herein,three iron(Ⅱ)complexes are designed to help us to understand the activation of CO_(2)and release of CO.Our research reveals that by removing one of the axial pyridine ligands from polypyridyl-iron(Ⅱ)complex 3,the favorable H2O coordination greatly decreases the activation energy of C-O bond cleavage of complex 1 and 2,and the resultant high-spin Fe(II)carbonyl intermediate with weaker ligand field dramatically reduces CO binding affinity and improves the faradaic efficiency from∼17%to 90%in catalytic CO_(2)RR.展开更多
基金supported by the National Key R&D Program of China(grant nos.2022YFA1502900,2022YFA0911900,and 2021YFA1500800)the National Natural Science Foundation of China(grant nos.22231001,21933007,22193013,and 22088102)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Science(grant no.XDB17000000)the New Cornerstone Science Foundation.
文摘In a carbon dioxide reduction reaction(CO_(2)RR),metal carbonyl intermediate not only serves as the 2e-/2H+reduction product,but it also contributes to CO release for catalyst regeneration.In the past decade,a large number of studies have demonstrated that a catalyst binds,activates,and achieves electron transfer to CO_(2).However,the formation of metal carbonyl intermediate and release of CO during the CO_(2)RR process have not received the same level of attention.Herein,three iron(Ⅱ)complexes are designed to help us to understand the activation of CO_(2)and release of CO.Our research reveals that by removing one of the axial pyridine ligands from polypyridyl-iron(Ⅱ)complex 3,the favorable H2O coordination greatly decreases the activation energy of C-O bond cleavage of complex 1 and 2,and the resultant high-spin Fe(II)carbonyl intermediate with weaker ligand field dramatically reduces CO binding affinity and improves the faradaic efficiency from∼17%to 90%in catalytic CO_(2)RR.
