Photocatalytic water oxidation reaction by transition metal complexes remains a challenge because of their poor stability under irradiation,especially for earth-abundant metal catalysts.In this regard,ironbased water ...Photocatalytic water oxidation reaction by transition metal complexes remains a challenge because of their poor stability under irradiation,especially for earth-abundant metal catalysts.In this regard,ironbased water oxidation catalysts are prone to hydrolysis and/or dissociate the ligands to form nanoparticles under a real catalytic condition.Herein,we describe a unique hexa-coordinated catalyst 1[Fe^(II)(Py_(3)tacn)Cl_(2)]and its reference 2[Fe^(II)(PhPy_(2)tacn)Cl_(2)]with a dangling pyridyl ligand and a phenyl group,respectively.We anticipated that the dynamically open and close coordination behaviors of the pyridyl ligand enabled balance of the reactivity and stability of catalyst 1.To our delight,the“open form”of catalyst 1 provided a free coordination site,and the“close form”guaranteed its molecular integrity,resulting in a water oxidation reaction with high efficiency and robustness.The turnover number and turnover frequency values of 2332 and 60 s^(−1)are the highest known to date among iron-based homogeneous water oxidation systems under visible light irradiation.展开更多
基金support from the National Key Research and Development Program of China(grant nos.2022YFA1502900,2022YFA0911900,2021YFA1500800,and 2022YFB3803600)the National Natural Science Foundation of China(grant nos.20231001,22201288,21933007,22193013,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Photocatalytic water oxidation reaction by transition metal complexes remains a challenge because of their poor stability under irradiation,especially for earth-abundant metal catalysts.In this regard,ironbased water oxidation catalysts are prone to hydrolysis and/or dissociate the ligands to form nanoparticles under a real catalytic condition.Herein,we describe a unique hexa-coordinated catalyst 1[Fe^(II)(Py_(3)tacn)Cl_(2)]and its reference 2[Fe^(II)(PhPy_(2)tacn)Cl_(2)]with a dangling pyridyl ligand and a phenyl group,respectively.We anticipated that the dynamically open and close coordination behaviors of the pyridyl ligand enabled balance of the reactivity and stability of catalyst 1.To our delight,the“open form”of catalyst 1 provided a free coordination site,and the“close form”guaranteed its molecular integrity,resulting in a water oxidation reaction with high efficiency and robustness.The turnover number and turnover frequency values of 2332 and 60 s^(−1)are the highest known to date among iron-based homogeneous water oxidation systems under visible light irradiation.
