Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO_(2) Reduction  

作　　者：Yuchen Wang Jihong Zhang Wei Yang Weixue Tao Keying Tao Jihua Deng Wenjie Shi Dichang Zhong Tongbu Lu 

机构地区：[1]MOE International Joint Laboratory of Materials Microstructure,Institute for New Energy Materials & Low Carbon Technologies, School of Material Science & Engineering,Tianjin University of Technology,Tianjin,300384 China [2]Guangdong Provincial Key Laboratory of Fuel Cell Technology,Guangzhou,Guangdong,510641 China

出　　处：《Chinese Journal of Chemistry》2023年第23期3305-3310,共6页中国化学（英文版）

基　　金：supported by the National Key R&D Program of China(2022YFA1502902);the National Natural Science Foundation of China(22271218,22071182,22201209,and 21931007);the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202210).

摘　　要：The creation of effective and inexpensive catalysts is essential for photocatalytic CO_(2) reduction.Homogeneous molecular catalysts,possessing definite crystal structures,are desirable to study the relationship between catalytic performance and coordination microenvironment around catalytic center.In this report,we elaborately developed three Co(II)-based molecular catalysts with different coordination microenvironments for CO_(2) reduction,named[CoN_(3)O]ClO_(4),[CoN_(4)]ClO_(4),and[CoN_(3)S]ClO_(4),respectively.The optimal[CoN_(3)O]ClO_(4) photocatalyst has a maximum TON of 5652 in photocatalytic reduced CO_(2) reduction,which is 1.28 and 1.65 times greater than that of[CoN_(4)]ClO_(4) and[CoN_(3)S]ClO_(4),respectively.The high electronegativity of oxygen in L1(N,N-bis(2-pyridylmethyl)-N-(2-hydroxybenzyl)amine)provides the Co(II)catalytic centers with low reduction potentials and a more stable*COOH intermediate,which facilitates the CO_(2)-to-CO conversion and accounts for the high photocatalytic activity of[CoN_(3)O]ClO_(4).This work provides researchers new insights in development of catalysts for photocatalytic CO_(2) reduction.

关 键 词：Co(II)-based homogeneous catalysts Coordination microenvironment PHOTOCATALYSIS CO_(2)reduction Homogenous catalysis 

分 类 号：O64[理学—物理化学]