Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-...Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-cost 2D MOFs constructed by a raw chemical succinic acid(SA),M-SA(M=Ni or Co),which served as efficient photocatalysts for the reduction of CO_(2)to CO.Taking advantage of the thinness and open metal sites,the ultrathin Ni-SA nanosheets(ca.3.6 nm)exhibited excellent CO production of 6.96(7)mmol·g^(−1)·h^(−1)and CO selectivity of 96.6%.Photoelectrochemical tests and theoretical calculations further confirmed the higher charge transfer efficiency and unsaturated metal sites for promoting photocatalytic performances.More importantly,Ni-SA can also be synthesized in large-scale by an energy-saving method under room temperature,strongly suggesting its promising future and potential for practical applications.展开更多
Design and construction of suitable pore microenvironments for selective catalytic reactions of small guest molecules is a major goal for chemists.Herein,we report control of competitive E–Z photoisomerization and ph...Design and construction of suitable pore microenvironments for selective catalytic reactions of small guest molecules is a major goal for chemists.Herein,we report control of competitive E–Z photoisomerization and photodimerization within porous metal–organic frameworks(MOFs)by fine-tuning the pore microenvironments using different dicarboxylate linkers.MOFs with small pores((E)-X_(MOF_(1))and(E)-X_(MOF_(1))′)favor the photoinduced E–Z isomerization of one encapsulated diaryl alkene substrate while those with large pores(((E)-X)_(2MOF_(2)))prefer the photodimerization of two encapsulated alkene substrates.Both reactions show broad functional group compatibility and proceed stereospecifically in good yields under mild conditions.High local concentration of diaryl alkene ligands and their preorientation within pores facilitate stereoselective dimerization.This pore engineering strategy is applicable to control and create pore microenvironemnts for other photoinduced organic reactions within porous MOFs.展开更多
基金Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM)(No.ZDSYS20210709112802010)China Postdoctoral Science Foundation(No.2022M711483).
文摘Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-cost 2D MOFs constructed by a raw chemical succinic acid(SA),M-SA(M=Ni or Co),which served as efficient photocatalysts for the reduction of CO_(2)to CO.Taking advantage of the thinness and open metal sites,the ultrathin Ni-SA nanosheets(ca.3.6 nm)exhibited excellent CO production of 6.96(7)mmol·g^(−1)·h^(−1)and CO selectivity of 96.6%.Photoelectrochemical tests and theoretical calculations further confirmed the higher charge transfer efficiency and unsaturated metal sites for promoting photocatalytic performances.More importantly,Ni-SA can also be synthesized in large-scale by an energy-saving method under room temperature,strongly suggesting its promising future and potential for practical applications.
基金the financial support of the National Natural Science Foundation of China(NSFCgrant nos.21961004,52002089,21531006,21773163)the China Postdoctoral Science Foundation(grant no.2020M670525).
文摘Design and construction of suitable pore microenvironments for selective catalytic reactions of small guest molecules is a major goal for chemists.Herein,we report control of competitive E–Z photoisomerization and photodimerization within porous metal–organic frameworks(MOFs)by fine-tuning the pore microenvironments using different dicarboxylate linkers.MOFs with small pores((E)-X_(MOF_(1))and(E)-X_(MOF_(1))′)favor the photoinduced E–Z isomerization of one encapsulated diaryl alkene substrate while those with large pores(((E)-X)_(2MOF_(2)))prefer the photodimerization of two encapsulated alkene substrates.Both reactions show broad functional group compatibility and proceed stereospecifically in good yields under mild conditions.High local concentration of diaryl alkene ligands and their preorientation within pores facilitate stereoselective dimerization.This pore engineering strategy is applicable to control and create pore microenvironemnts for other photoinduced organic reactions within porous MOFs.
