Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) mol...Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) molecule is a thermodynamically uphill process,which involves multiple elemental steps and the competition of hydrogen evolution reaction(HER) in aqueous solution.展开更多
Transition metal oxides are promising candidates for the high-capacity anode material in lithium-ion batteries.The electrochemical performance of transition metal oxides can be improved by constructing suitable compos...Transition metal oxides are promising candidates for the high-capacity anode material in lithium-ion batteries.The electrochemical performance of transition metal oxides can be improved by constructing suitable composite architectures. Herein, we demonstrate a metal–organic framework(MOF)-assisted strategy for the synthesis of a hierarchical hybrid nanostructure composed of Fe_2O_3 nanotubes assembled in Co_3O_4 host. Starting from MOF composite precursors(Fe-based MOF encapsulated in a Cobased host matrix), a complex structure of Co_3O_4 host and engulfed Fe_2O_3 nanotubes was prepared by a simple annealing treatment in air. By virtue of their structural and compositional features, these hierarchical composite particles reveal enhanced lithium storage properties when employed as anodes for lithium-ion batteries.展开更多
The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growt...The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.展开更多
The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex...The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.展开更多
By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction anal...By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group P2/c, a = 13.4224（18）, b = 13.759（2）, c = 8.0633（17）/~, fl = 96.448（3）~, C23H23NsNi（NO3）2, M,. = 552.19, V = 1479.7（4） A3, Z = 2, Dc = 1.239 g/cm3,/ffMoKa） = 0.700 mm-1, F（000） = 572, the final R = 0.0566 and wR = 0.1336 for 1638 observed reflections with I 〉 2a（/）. X-ray analysis indicates that each metal center coordinates with two N and two H atoms in tetrahedral interaction geometry. Weak interaction between Ni and N atom of pyrazole ligand and agostic bond （Ni...H-N interaction） play important roles in the formation of the 2-dimension framework. Significantly, this framework could pack into a tubular channel with NO3 anions trapped inside.展开更多
A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized un...A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.展开更多
To expand the use of metal–organic frameworks(MOFs)based self-lubricating composite,flexible MOFs MIL-88D has been studied as a nanocontainer for loading lubricant.In this work,the mechanism of oleamine adsorption an...To expand the use of metal–organic frameworks(MOFs)based self-lubricating composite,flexible MOFs MIL-88D has been studied as a nanocontainer for loading lubricant.In this work,the mechanism of oleamine adsorption and desorption by MIL-88D was investigated through molecular simulations and experiments.Molecular simulations showed that the oleamines can be physically adsorbed into open MIL-88Ds with the Fe and O atoms of MIL-88D interacting with oleamine NH2-group.Higher temperature can cause Ole@MIL-88D to release more oleamines,while higher pressure on Ole@MIL-88D caused less oleamines released.Moreover the Ole@MIL-88D was incorporated into epoxy resin(EP)for friction tests.The optimum mass ratio of MIL-88D to EP is 15 wt%,and the EP/Ole@MIL-88D prefers light load and high frequency friction.This work suggests that flexible MOFs can be used as a nanocontainer for loading lubricant,and can be used as a new self-lubricating composite.展开更多
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
Discovering more and new geometrically frustrated systems remains an active point of inquiry in fundamental physics for the existence of unusual states of matter.Here,we report spin-liquid-like behavior in a two-dimen...Discovering more and new geometrically frustrated systems remains an active point of inquiry in fundamental physics for the existence of unusual states of matter.Here,we report spin-liquid-like behavior in a two-dimensional(2D)rhombic lattice Fe-metal-organic framework(Fe-MOF)with frustrated antiferromagnetism.This Fe-MOF exhibits a high frustration factor f=|θCW|/TN≥315,and its long-range magnetic order is suppressed down to 180 mK.Detailed theoretical calculations demonstrate strong antiferromagnetic coupling between adjacent Fe3+ions,indicating the potential of a classical spin-liquid-like behavior.Notably,a T-linear heat capacity parameter,γ,originating from electronic contributions and with magnetic field independence up to 8 T,can be observed in the specific heat capacity measurements at low-temperature,providing further proof for the spin-liquid-like behavior.This work highlights the potential of MOF materials in geometrically frustrated systems,and will promote the research of exotic quantum physics phenomena.展开更多
基金supported by the National Natural Science Foundation of China(21875030,21908120)the Liaoning Excellent Talents in University(LR2019016)。
文摘Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) molecule is a thermodynamically uphill process,which involves multiple elemental steps and the competition of hydrogen evolution reaction(HER) in aqueous solution.
文摘Transition metal oxides are promising candidates for the high-capacity anode material in lithium-ion batteries.The electrochemical performance of transition metal oxides can be improved by constructing suitable composite architectures. Herein, we demonstrate a metal–organic framework(MOF)-assisted strategy for the synthesis of a hierarchical hybrid nanostructure composed of Fe_2O_3 nanotubes assembled in Co_3O_4 host. Starting from MOF composite precursors(Fe-based MOF encapsulated in a Cobased host matrix), a complex structure of Co_3O_4 host and engulfed Fe_2O_3 nanotubes was prepared by a simple annealing treatment in air. By virtue of their structural and compositional features, these hierarchical composite particles reveal enhanced lithium storage properties when employed as anodes for lithium-ion batteries.
基金supported by National Natural Science Foundation of China(21878062)
文摘The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.
基金Supported by Nanjing University of Posts and Telecommunications (No. NY209032)the National Natural Science Foundation of China (No. 21001065)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.
基金supported by the Natural Science Foundation of Zhejiang Province(Y5080308)
文摘By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group P2/c, a = 13.4224（18）, b = 13.759（2）, c = 8.0633（17）/~, fl = 96.448（3）~, C23H23NsNi（NO3）2, M,. = 552.19, V = 1479.7（4） A3, Z = 2, Dc = 1.239 g/cm3,/ffMoKa） = 0.700 mm-1, F（000） = 572, the final R = 0.0566 and wR = 0.1336 for 1638 observed reflections with I 〉 2a（/）. X-ray analysis indicates that each metal center coordinates with two N and two H atoms in tetrahedral interaction geometry. Weak interaction between Ni and N atom of pyrazole ligand and agostic bond （Ni...H-N interaction） play important roles in the formation of the 2-dimension framework. Significantly, this framework could pack into a tubular channel with NO3 anions trapped inside.
基金Supported by the Foundation for Science&Technology Innovation Talents in Henan Province(Nos.14HASTIT014,and 16410010012)Natural Science Foundation of China(Nos.21671114)the Foundation of Education Committee of Henan province,China(No.14B150033)
文摘A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.
基金Foundation of State Key Laboratory of Tribology in Advanced Equipment at Tsinghua University(Grant No.SKLTKF21B13)Natural Science Foundation of Hebei Province of China(Grant No.E2021203092)National Natural Science Foundation of China(Grant No.51905297)are acknowledged.
文摘To expand the use of metal–organic frameworks(MOFs)based self-lubricating composite,flexible MOFs MIL-88D has been studied as a nanocontainer for loading lubricant.In this work,the mechanism of oleamine adsorption and desorption by MIL-88D was investigated through molecular simulations and experiments.Molecular simulations showed that the oleamines can be physically adsorbed into open MIL-88Ds with the Fe and O atoms of MIL-88D interacting with oleamine NH2-group.Higher temperature can cause Ole@MIL-88D to release more oleamines,while higher pressure on Ole@MIL-88D caused less oleamines released.Moreover the Ole@MIL-88D was incorporated into epoxy resin(EP)for friction tests.The optimum mass ratio of MIL-88D to EP is 15 wt%,and the EP/Ole@MIL-88D prefers light load and high frequency friction.This work suggests that flexible MOFs can be used as a nanocontainer for loading lubricant,and can be used as a new self-lubricating composite.
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supported by the National Key Research and Development Program of China(No.2021YFA1600800)the National Natural Science Foundation of China(Nos.11975234,12075243,12005227,12105286,121350122,U2032150,12275271,12205305,and U1932211)+5 种基金the Natural Science Foundation of Anhui Province(Nos.2208085QA14 and 2208085J13)the Users with Excellence Program of Hefei Science Center CAS(Nos.2020HSC-UE002,2020HSC-CIP013,2021HSC-UE002,and 2021HSC-UE003)the Major science and technology project of Anhui Province(No.202103a05020025)the Key Program of Research and Development of Hefei Science Center,CAS(Nos.2021HSC-KPRD002 and 2021HSC-KPRD003)the Fundamental Research Funds for the Central Universities(No.WK 2310000103)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication.
文摘Discovering more and new geometrically frustrated systems remains an active point of inquiry in fundamental physics for the existence of unusual states of matter.Here,we report spin-liquid-like behavior in a two-dimensional(2D)rhombic lattice Fe-metal-organic framework(Fe-MOF)with frustrated antiferromagnetism.This Fe-MOF exhibits a high frustration factor f=|θCW|/TN≥315,and its long-range magnetic order is suppressed down to 180 mK.Detailed theoretical calculations demonstrate strong antiferromagnetic coupling between adjacent Fe3+ions,indicating the potential of a classical spin-liquid-like behavior.Notably,a T-linear heat capacity parameter,γ,originating from electronic contributions and with magnetic field independence up to 8 T,can be observed in the specific heat capacity measurements at low-temperature,providing further proof for the spin-liquid-like behavior.This work highlights the potential of MOF materials in geometrically frustrated systems,and will promote the research of exotic quantum physics phenomena.
