It is highly desirable to mimic the ratchet-like multi-electron transfer of the electron transport chain(ETC)by artificial systems and impose dual-mode anaerobic denitrification and aerobic oxidation on organic compou...It is highly desirable to mimic the ratchet-like multi-electron transfer of the electron transport chain(ETC)by artificial systems and impose dual-mode anaerobic denitrification and aerobic oxidation on organic compounds to produce value-added fine chemicals.However,the extreme complexity of biological structures hampers their direct mimicry.In this article,we report a new continuous and directional photoinduced-electron transfer(PET)method to mimic the ETC process of natural enzymes using metal–organic frameworks(MOFs)as the platform.展开更多
In addition to their many well-known advantages(e.g.,ultra-high porosity,good pore size distribution,easy functionalization,and structural tolerability),metal-organic frameworks(MOFs)are a new class of advanced functi...In addition to their many well-known advantages(e.g.,ultra-high porosity,good pore size distribution,easy functionalization,and structural tolerability),metal-organic frameworks(MOFs)are a new class of advanced functional materials.However,their backbones are highly susceptible to deformation after exposure to acidic or alkaline conditions.As a result of lithium-ion batteries embedding or detaching directly from MOFs,they irreversibly collapse.As a result,they fail to maintain their electrochemical performance.These factors have hindered the development of MOFs as direct electrode materials,making the design of MOF materials with controlled morphology and stable dimensions a new challenge.In this study,we adopted a versatile and effective method to synthesize a novel MOF material(NiCo-BP(BP=BTC/phen and BTC=1,3,5-benzenetricarboxylic acid))using the rigid ligands 1,10-phenanthroline and homobenzotrizoic acid,and the emergence of the Ni-O/N and Co-O/N coordination layers was observed by extended X-ray absorption fine structure(EXAFS)tests,indicating that Ni and Co were coordinated with heterocyclic N-given atoms to form a stable p-πconjugated structure.Meanwhile,the metal-ion is attached to the carboxylic acid ligand on the other side,making the metal-organic skeleton complete and robust.The nanosphere structure of NiCo-BP(~400 nm)allows for full exposure and utilisation of the active sites,especially the Ni,Co,and phenanthroline units,and exhibit impressively high specific capacity and cycling stability.At a high current density of 1.0 A·g^(−1),a high discharge specific capacity of 631.6 mAh·g^(−1)was obtained after 1000 cycles.The co-participation of two organic ligands in the coordination is in accordance with the theory of soft and hard acids and bases,which contributes to the ability of the material to maintain a high capacity in cycling as well as its cyclic stability.展开更多
基金funded by the National Natural Science Foundation of China(No.22472020,22301028,21971031,21820102001,21231003)Liaoning Province Science and Technology Plan Joint Project(No.2023JH2/101700297)+2 种基金Foreign Youth Talent Program(No.QN2023127001L)Fundamental Research Funds for the Central Universities(No.DUT24YG123)Our special thanks to Dr Rui Cai,Dr Dan Wang,and Dr Liyan Zhang at the Instrumental Analysis Center and State Key Laboratory of Fine Chemicals,Dalian University of Technology,for their assistance with experiments and analyses on the fluorescence,EPR,and ground-state UV/vis/IR absorption studies,respectively.
文摘It is highly desirable to mimic the ratchet-like multi-electron transfer of the electron transport chain(ETC)by artificial systems and impose dual-mode anaerobic denitrification and aerobic oxidation on organic compounds to produce value-added fine chemicals.However,the extreme complexity of biological structures hampers their direct mimicry.In this article,we report a new continuous and directional photoinduced-electron transfer(PET)method to mimic the ETC process of natural enzymes using metal–organic frameworks(MOFs)as the platform.
基金National Natural Science Foundation of China(Nos.52071132,52261135632,U21A20284,and 52371237)Program for Innovative Team(in Science and Technology)in University of Henan Province,China(No.24IRTSTHN006)+3 种基金Natural Science Foundation of Henan,China(Nos.232300421080 and 222300420138)Science and Technology Project of Henan Province,China(Nos.232102241038 and 232102241004)Key Scientific Research Programs in Universities of Henan Province,China-Special Projects for Basic Research(No.23ZX008)Innovative Funds Plan of Henan University of Technology,China(No.2020ZKCJ04).
文摘In addition to their many well-known advantages(e.g.,ultra-high porosity,good pore size distribution,easy functionalization,and structural tolerability),metal-organic frameworks(MOFs)are a new class of advanced functional materials.However,their backbones are highly susceptible to deformation after exposure to acidic or alkaline conditions.As a result of lithium-ion batteries embedding or detaching directly from MOFs,they irreversibly collapse.As a result,they fail to maintain their electrochemical performance.These factors have hindered the development of MOFs as direct electrode materials,making the design of MOF materials with controlled morphology and stable dimensions a new challenge.In this study,we adopted a versatile and effective method to synthesize a novel MOF material(NiCo-BP(BP=BTC/phen and BTC=1,3,5-benzenetricarboxylic acid))using the rigid ligands 1,10-phenanthroline and homobenzotrizoic acid,and the emergence of the Ni-O/N and Co-O/N coordination layers was observed by extended X-ray absorption fine structure(EXAFS)tests,indicating that Ni and Co were coordinated with heterocyclic N-given atoms to form a stable p-πconjugated structure.Meanwhile,the metal-ion is attached to the carboxylic acid ligand on the other side,making the metal-organic skeleton complete and robust.The nanosphere structure of NiCo-BP(~400 nm)allows for full exposure and utilisation of the active sites,especially the Ni,Co,and phenanthroline units,and exhibit impressively high specific capacity and cycling stability.At a high current density of 1.0 A·g^(−1),a high discharge specific capacity of 631.6 mAh·g^(−1)was obtained after 1000 cycles.The co-participation of two organic ligands in the coordination is in accordance with the theory of soft and hard acids and bases,which contributes to the ability of the material to maintain a high capacity in cycling as well as its cyclic stability.
