Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and...Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and functional groups.Herein,we report the catalytic efficiency of an amino‐acid‐based Cu‐containing MOF,denoted as CuTrp(Trp=L‐tryptophan).The CuTrp catalyst was synthesized by direct mixing at room temperature using methanol as a solvent-a synthetic route with notable energy efficiency.The catalyst was characterized using various physicochemical techniques,including XRD,FT‐IR,TGA,XPS,ICP‐OES,FE‐SEM,and BET analysis.The catalytic activity of CuTrp was assessed in the synthesis of cyclic carbonates from epoxides and CO2.The CuTrp operated in synergy with the co‐catalyst tetrabutylammonium bromide under solvent‐free conditions.Several reaction parameters were studied to identify the optimal reaction conditions and a reaction mechanism was proposed based on experimental evidence and previous density functional theory studies.The CuTrp also exhibited satisfactory stability in water and could be reused more than three times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robus...Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.展开更多
Organic carbonates(OCs)are a class of compounds featured by a carbonyl flanked by two alkoxy/aryloxy groups.They exist in either linear or cyclic forms,of which the majority encountered in nature adopt a pentacyclic s...Organic carbonates(OCs)are a class of compounds featured by a carbonyl flanked by two alkoxy/aryloxy groups.They exist in either linear or cyclic forms,of which the majority encountered in nature adopt a pentacyclic structure.However,the enzymatic basis for pentacyclic carbonate ring formation remains elusive.Here,we reported that a four-protein metabolon(AlmUII-UV)assembled by a small peptide protein(AlmUV)appends a reactive N-hydroxylcarbamoyl moiety to the decarboxylated aldgamycins followed by a non-enzymatic condensation to give the pentacyclic carbonate ring.Our results have documented an unprecedent mechanism for carbonate formation.展开更多
文摘Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and functional groups.Herein,we report the catalytic efficiency of an amino‐acid‐based Cu‐containing MOF,denoted as CuTrp(Trp=L‐tryptophan).The CuTrp catalyst was synthesized by direct mixing at room temperature using methanol as a solvent-a synthetic route with notable energy efficiency.The catalyst was characterized using various physicochemical techniques,including XRD,FT‐IR,TGA,XPS,ICP‐OES,FE‐SEM,and BET analysis.The catalytic activity of CuTrp was assessed in the synthesis of cyclic carbonates from epoxides and CO2.The CuTrp operated in synergy with the co‐catalyst tetrabutylammonium bromide under solvent‐free conditions.Several reaction parameters were studied to identify the optimal reaction conditions and a reaction mechanism was proposed based on experimental evidence and previous density functional theory studies.The CuTrp also exhibited satisfactory stability in water and could be reused more than three times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金supported by the National Key R&D Program of China(2017YFA0700102)the National Natural Science Foundation of China(21573222 and 91545202)+1 种基金the Outstanding Youth Talent Project of Dalian(2017RJ03)the DMTO Project of Dalian Institute of Chemical Physics,CAS(DICP DMTO201702),the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200),the Youth Innovation Promotion Association,CAS(2015145)~~
文摘Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.
基金financially supported by grants from National Key Research and Development Program of China(2018YFA0903200/2018YFA0903201)the National Natural Science Foundation of China(81925037,31870032,31761143016 and 31670036)+7 种基金the 111 Project of Ministry of Education of the People’s Republic of China(B13038)Chang Jiang Scholars Program(Young Scholar)from the Ministry of Education of China(Hao Gao,2017)National High-level Personnel of Special Support Program(2017RA2259,China)the Guangdong Natural Science Funds for Distinguished Young Scholar(2019B151502014,China)Guangdong Special Support Program(2016TX03R280,China)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Y036,China)K.C.Wong Education Foundation(Hao Gao,2016,China)China Postdoctoral Science Foundation(2019M663192)
文摘Organic carbonates(OCs)are a class of compounds featured by a carbonyl flanked by two alkoxy/aryloxy groups.They exist in either linear or cyclic forms,of which the majority encountered in nature adopt a pentacyclic structure.However,the enzymatic basis for pentacyclic carbonate ring formation remains elusive.Here,we reported that a four-protein metabolon(AlmUII-UV)assembled by a small peptide protein(AlmUV)appends a reactive N-hydroxylcarbamoyl moiety to the decarboxylated aldgamycins followed by a non-enzymatic condensation to give the pentacyclic carbonate ring.Our results have documented an unprecedent mechanism for carbonate formation.
