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
Technological application of the electrochemical reduction of CO_(2)relies on efficient electrocatalysts.We demonstrate that the introduction of amino groups alongside the porphyrin cobalt centers in a metal-organic f...Technological application of the electrochemical reduction of CO_(2)relies on efficient electrocatalysts.We demonstrate that the introduction of amino groups alongside the porphyrin cobalt centers in a metal-organic framework(MOF)can dramatically accelerate the electrochemical CO_(2)reduction performance.A classic cobalt porphyrin-based MOF showing moderate CO_(2)-to-CO electroreduction performance(turnover frequency[TOF]=0.20 s^(−1),Faradic efficiency[FE]=47.4%)is modified.By molecular design of the porphyrin-based ligand,amino groups are introduced alongside the cobalt center,giving remarkably enhanced CO_(2)-to-CO electroreduction performance as high as FE 99.4%,current density 7.2 mA cm^(−2),and TOF 21.17 s^(−1),in a nearneutral aqueous solution at a low overpotential of 525 mV.Density functional theory calculations showed that the prepositioned amino groups,although located not sufficiently close to the active center,serve as hydrogen-bonding donors to stabilize the intermediate Co-CO_(2)adduct and impede the formation of Co-H_(2)O adduct,which not only promotes the CO_(2)reduction reaction but also restrains the hydrogen evolution reaction.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This research was supported by the National Key Research and Development Program of China(grant no.2021YFA1500401)the National Natural Science Foundation of China(grant nos.21890380,21821003,22071272,21975290,and 21731007)+1 种基金the Guangdong Pearl River Talents Program(grant no.2017BT01C161)the Guangdong Natural Science Funds for Distinguished Young Scholar(grant no.2018B030306009).
文摘Technological application of the electrochemical reduction of CO_(2)relies on efficient electrocatalysts.We demonstrate that the introduction of amino groups alongside the porphyrin cobalt centers in a metal-organic framework(MOF)can dramatically accelerate the electrochemical CO_(2)reduction performance.A classic cobalt porphyrin-based MOF showing moderate CO_(2)-to-CO electroreduction performance(turnover frequency[TOF]=0.20 s^(−1),Faradic efficiency[FE]=47.4%)is modified.By molecular design of the porphyrin-based ligand,amino groups are introduced alongside the cobalt center,giving remarkably enhanced CO_(2)-to-CO electroreduction performance as high as FE 99.4%,current density 7.2 mA cm^(−2),and TOF 21.17 s^(−1),in a nearneutral aqueous solution at a low overpotential of 525 mV.Density functional theory calculations showed that the prepositioned amino groups,although located not sufficiently close to the active center,serve as hydrogen-bonding donors to stabilize the intermediate Co-CO_(2)adduct and impede the formation of Co-H_(2)O adduct,which not only promotes the CO_(2)reduction reaction but also restrains the hydrogen evolution reaction.
