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 betwe...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.展开更多
Metal-organic frameworks(MOFs) as a type of crystalline heterogeneous catalysts have shown potential application in photocatalytic CO_(2)reduction.However,MOF catalysts with high efficiency and selectivity are still i...Metal-organic frameworks(MOFs) as a type of crystalline heterogeneous catalysts have shown potential application in photocatalytic CO_(2)reduction.However,MOF catalysts with high efficiency and selectivity are still in pursuit.Herein,by a bimetallic strategy,the catalytic performance of a Co-MOF for photocatalytic CO_(2)reduction was enhanced.Specifically,the Co-MOF based on 4,5-dicarboxylic acid(H;IDC) and4,4’-bipydine(4,4’-bpy) can catalyze CO;reduction to CO,with high efficiency but relatively low selectivity.After replacement of 2/3 Co(Ⅱ) with Ni(Ⅱ) within Co-MOF,the resulted isostructural Co_(1)Ni_(2)-MOF not only retains high efficiency for photocatalytic CO_(2)reduction,but also shows enhanced CO selectivity.The CO evolution rate reaches 1160 μmol g^(-1)h^(-1)and the CO selectivity reaches as high as 94.6%.The enhanced photocatalytic CO_(2)reduction performance is supported by theoretical calculation results.This case demonstrates that bimetallic strategy is an effective mean to optimize the catalytic performance of MOF catalysts for photochemical CO_(2)reduction.展开更多
基金supported by the National Key R&D Program of China(2017YFA0700104)the National Natural Science Foundation of China(22071182,21861001,21931007 and 21790052)+1 种基金the 111 Project of China(D17003)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ129).
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).
文摘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.
基金financially supported by the National Key R&D Program of China (No. 2017YFA0700104)the National Natural Science Foundation of China (Nos. 22071182, 21861001, 21931007 and21790052)+1 种基金the 111 Project of China (No. D17003)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education (No. 2018KJ129)。
文摘Metal-organic frameworks(MOFs) as a type of crystalline heterogeneous catalysts have shown potential application in photocatalytic CO_(2)reduction.However,MOF catalysts with high efficiency and selectivity are still in pursuit.Herein,by a bimetallic strategy,the catalytic performance of a Co-MOF for photocatalytic CO_(2)reduction was enhanced.Specifically,the Co-MOF based on 4,5-dicarboxylic acid(H;IDC) and4,4’-bipydine(4,4’-bpy) can catalyze CO;reduction to CO,with high efficiency but relatively low selectivity.After replacement of 2/3 Co(Ⅱ) with Ni(Ⅱ) within Co-MOF,the resulted isostructural Co_(1)Ni_(2)-MOF not only retains high efficiency for photocatalytic CO_(2)reduction,but also shows enhanced CO selectivity.The CO evolution rate reaches 1160 μmol g^(-1)h^(-1)and the CO selectivity reaches as high as 94.6%.The enhanced photocatalytic CO_(2)reduction performance is supported by theoretical calculation results.This case demonstrates that bimetallic strategy is an effective mean to optimize the catalytic performance of MOF catalysts for photochemical CO_(2)reduction.
