Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable bat...Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable batteries(ASIBs),which operate in aqueous electrolytes,are cheaper,safer,and more ionically conductive than batteries that operate in conventional organic electrolytes;furthermore,they are suitable for grid-scale energy storage applications.As electrode materials for storing Na~+ ions in ASIBs,a variety of multifunctional metal-organic frameworks(MOFs) have demonstrated great potential in terms of having porous 3 D crystal structures,compatibility with aqueous solutions,long cycle lives(≥1000 cycles),and ease of synthesis.The present review describes MOF-derived technologies for the successful application of MOFs to ASIBs and suggests future challenges in this area of research based on the current understanding.展开更多
A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had...A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had excellent selectivity and repeatability for Hg(Ⅱ),the optimum pH was 3.0,the maximum adsorption capacity was 872.8 mg/g,and the process was a spontaneous exothermic reaction.The adsorption behavior was chemisorption,which conformed to the pseudo-second-order kinetic and Freundlich isothermal model.Moreover,the adsorption mechanism showed that the adsorption process mainly depended on ion exchange and chelation,and the synergistic action of S and N atoms played a key role.So,MTZ-MOFs were an efficient adsorbent for mercury ion removal.展开更多
The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),wer...The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),were investigated in a batch adsorption system as a function of initial pH, adsorbent concentration, contact time, initial dye concentration, and temperature. The Langmuir, Freundlich, and DubininRadushkevich( D-R) isotherm models were used for modeling the adsorption equilibrium. It was found that Langmuir model yielded a much better fit than the Freundlich model under different temperatures. The maximum monolayer adsorption capacities of MB were 192. 98,229. 86,and 297. 38 mg /g at 298,308,and 318 K,respectively. The calculated mean adsorption energy( 8. 26-11. 04 kJ /mol) using D-R model indicated that the adsorption process might take place by chemical adsorption mechanism.Otherwise,the kinetic studies revealed that the adsorption process could be well explained by pseudo-second-order rate kinetics and intraparticle diffusion was not the rate-limiting step.Thermodynamic studies indicated that this system was feasible,spontaneous,and endothermic process. Based on these studies,H2dtoaCu can be considered as a potential adsorbent for the removal of MB from aqueous solution.展开更多
Sorption isotherms of methane and hydrogen on Cu3(BTC)2 have been measured in the temperature range from 273 to 318 K and at pressures up to 15 MPa. H2 excess sorption capacities of the Cu3(BTC)2 amounted to 3.9 mg/g ...Sorption isotherms of methane and hydrogen on Cu3(BTC)2 have been measured in the temperature range from 273 to 318 K and at pressures up to 15 MPa. H2 excess sorption capacities of the Cu3(BTC)2 amounted to 3.9 mg/g at 14 MPa. Promising maximum CH4 excess sorption capacities on the same sample were reached at approximately 5 MPa. They amounted to 101, 100, 92 and 80 mg/g at 273, 278, 293 and 318 K, respectively. The sorbed phase density was essestially the same for all temperatures and amounted to ~600 kg/m3. Structural changes of the Cu3(BTC)2 samples after thermal activation and treatment with high pressure H2 and CH4 were tested. It was found that the initial micropore structure has virtually disappeared as evidenced by a decrease of the Langmuir specific surface area by a factor ~3 and CO2 micropore volume by a factor of ~4 for H2 and ~3 for CH4. This is in line with an increase in the average pore diameter from initially 9.2 to 15.7 for H2 and 12.8 for CH4.展开更多
Electromagnetic pollution has been causing a series of problems in people’s life,and electromagnetic absorbers with lightweight and broad absorbing bandwidth properties are widely desired.In this work,novel sandwich-...Electromagnetic pollution has been causing a series of problems in people’s life,and electromagnetic absorbers with lightweight and broad absorbing bandwidth properties are widely desired.In this work,novel sandwich-like 2D laminated Fe&TiO2 nanoparticles@C nanocomposites were rationally designed and successfully developed from the MXene–MOFs hybrids.The formation of Fe and rutile-TiO2 nanoparticles sandwiched by the two-dimensional carbon nanosheets provided strong electromagnetic energy attenuation and good impedance matching for electromagnetic wave(EMW)absorption.As expected,the nanocomposites achieved a broad effective absorption bandwidth of 6.5 GHz at a thickness of only 1.6 mm and the minimum reflection loss(RL)value of−51.8 dB at 6.6 GHz with a thickness of 3 mm.This work not only provides a good design and fabricating concept for the laminated metal and functional nanoparticles@C nanocomposites with good EMW absorption,but also offers an important guideline to fabricate various two-dimensional nanocomposites derived from the MXene precursors.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 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
A novel metal-organic framework（MOF） compound of Pb（C5H4NCOO）2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell： orthorhombic space group Pccn,...A novel metal-organic framework（MOF） compound of Pb（C5H4NCOO）2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell： orthorhombic space group Pccn, a=1.0325（2） nm, b=1.3597（3） nm, c=0.8499（2） nm, V=1.1931（4） nm^3, Z=4, Dc=2.513 g/cm^3, R1=0.047 were obtained on the basis of 1365 reflections with Fo〉2σ（Fo）. PbN2O6 polyhedron adopts the distorted cubic configuration which is assigned to the holodirected geometry. These PbN2O6 polyhedra can form the zigzag chain by edge-sharing mode along（001） direction. Pb atom is connected by six nicotinic acid molecules, leading neutral 3D metal-organic framework with a channel defined by four Pb atoms and four nicotinic acid molecules.展开更多
The development of novel porous materials have attracted significant attention owing to its possible application in several fields.In this study,we designed a novel covalent organic framework‐metal‐organic framework...The development of novel porous materials have attracted significant attention owing to its possible application in several fields.In this study,we designed a novel covalent organic framework‐metal‐organic framework(COF‐MOF)material through an in‐situ ligand self‐assembly method.The in‐situ modified ligands not only act as nucleation sites to form Ti‐MOF,but also as a channel to rapidly transfer photogenerated electrons without introducing additional chemical bonds.The photocatalytic hydrogen production rate achieved over B‐CTF‐Ti‐MOF(1:1)was 1975μmol·g^(–1)·h^(–1) with an apparent quantum efficiency of 4.76%,which is 11.8 times higher than that of the pure CTF‐1.In addition,compared with the sample prepared by separating the ligands(CTF‐1/Ti‐MOF),B‐CTF‐Ti‐MOF shows excellent activity and stability.Finally,a reasonable photocatalytic mechanism was proposed using the results of electrochemical tests and spectral analyses.This study provides a universal method for the construction of highly efficient and stable COF/MOF materials with excellent properties.展开更多
基金supported by a National Research Foundation of Korea, South Korea (NRF) grant funded by the Korean government (MSITMinistry of Science and ICT+1 种基金Information and Communications Technologies) (NRF-2019R1F1A1042080)the Hallym University, South Korea Research Fund, 2019 (HRF-201912-013)。
文摘Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable batteries(ASIBs),which operate in aqueous electrolytes,are cheaper,safer,and more ionically conductive than batteries that operate in conventional organic electrolytes;furthermore,they are suitable for grid-scale energy storage applications.As electrode materials for storing Na~+ ions in ASIBs,a variety of multifunctional metal-organic frameworks(MOFs) have demonstrated great potential in terms of having porous 3 D crystal structures,compatibility with aqueous solutions,long cycle lives(≥1000 cycles),and ease of synthesis.The present review describes MOF-derived technologies for the successful application of MOFs to ASIBs and suggests future challenges in this area of research based on the current understanding.
基金supported by the Hubei Provincial Department of Education Science and Technology Research Program Young Talent Project,China (No. Q20201102)the National Natural Science Foundation of China (Nos. 51864042, 51804220)
文摘A novel adsorbent(MTZ-MOFs)was synthesized by a one-step reaction of zinc nitrate hexahydrate and 1-(2-dimethylaminoethyl)-1H-5-mercaptotetrazole to remove mercury from waste water.The results showed that MTZ-MOFs had excellent selectivity and repeatability for Hg(Ⅱ),the optimum pH was 3.0,the maximum adsorption capacity was 872.8 mg/g,and the process was a spontaneous exothermic reaction.The adsorption behavior was chemisorption,which conformed to the pseudo-second-order kinetic and Freundlich isothermal model.Moreover,the adsorption mechanism showed that the adsorption process mainly depended on ion exchange and chelation,and the synergistic action of S and N atoms played a key role.So,MTZ-MOFs were an efficient adsorbent for mercury ion removal.
基金National Key Technologies R&D Program of China during the 12th Five-Year Plan Period(No.2012BAD29B06,No2012BAK01B01)National Natural Science Foundation of China(No.21375021)+2 种基金Major Project of Fujian Provincial Science and Technology Program,China(No.2011N5008)Natural Science Foundation of Fujian Province of China(No.2012J05023)Program for New Century Excellent Talents in Fujian Province University,China(No.JA10011)
文摘The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),were investigated in a batch adsorption system as a function of initial pH, adsorbent concentration, contact time, initial dye concentration, and temperature. The Langmuir, Freundlich, and DubininRadushkevich( D-R) isotherm models were used for modeling the adsorption equilibrium. It was found that Langmuir model yielded a much better fit than the Freundlich model under different temperatures. The maximum monolayer adsorption capacities of MB were 192. 98,229. 86,and 297. 38 mg /g at 298,308,and 318 K,respectively. The calculated mean adsorption energy( 8. 26-11. 04 kJ /mol) using D-R model indicated that the adsorption process might take place by chemical adsorption mechanism.Otherwise,the kinetic studies revealed that the adsorption process could be well explained by pseudo-second-order rate kinetics and intraparticle diffusion was not the rate-limiting step.Thermodynamic studies indicated that this system was feasible,spontaneous,and endothermic process. Based on these studies,H2dtoaCu can be considered as a potential adsorbent for the removal of MB from aqueous solution.
文摘Sorption isotherms of methane and hydrogen on Cu3(BTC)2 have been measured in the temperature range from 273 to 318 K and at pressures up to 15 MPa. H2 excess sorption capacities of the Cu3(BTC)2 amounted to 3.9 mg/g at 14 MPa. Promising maximum CH4 excess sorption capacities on the same sample were reached at approximately 5 MPa. They amounted to 101, 100, 92 and 80 mg/g at 273, 278, 293 and 318 K, respectively. The sorbed phase density was essestially the same for all temperatures and amounted to ~600 kg/m3. Structural changes of the Cu3(BTC)2 samples after thermal activation and treatment with high pressure H2 and CH4 were tested. It was found that the initial micropore structure has virtually disappeared as evidenced by a decrease of the Langmuir specific surface area by a factor ~3 and CO2 micropore volume by a factor of ~4 for H2 and ~3 for CH4. This is in line with an increase in the average pore diameter from initially 9.2 to 15.7 for H2 and 12.8 for CH4.
基金supported by the National Natural Science Foundation of China(Nos.51971162,U1933112,51671146)the Program of Shanghai Technology Research Leader(18XD1423800)the Fundamental Research Funds for the Central Universities(22120180096)
文摘Electromagnetic pollution has been causing a series of problems in people’s life,and electromagnetic absorbers with lightweight and broad absorbing bandwidth properties are widely desired.In this work,novel sandwich-like 2D laminated Fe&TiO2 nanoparticles@C nanocomposites were rationally designed and successfully developed from the MXene–MOFs hybrids.The formation of Fe and rutile-TiO2 nanoparticles sandwiched by the two-dimensional carbon nanosheets provided strong electromagnetic energy attenuation and good impedance matching for electromagnetic wave(EMW)absorption.As expected,the nanocomposites achieved a broad effective absorption bandwidth of 6.5 GHz at a thickness of only 1.6 mm and the minimum reflection loss(RL)value of−51.8 dB at 6.6 GHz with a thickness of 3 mm.This work not only provides a good design and fabricating concept for the laminated metal and functional nanoparticles@C nanocomposites with good EMW absorption,but also offers an important guideline to fabricate various two-dimensional nanocomposites derived from the MXene precursors.
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 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 National Natural Science Foundation of China(No.20571032)
文摘A novel metal-organic framework（MOF） compound of Pb（C5H4NCOO）2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell： orthorhombic space group Pccn, a=1.0325（2） nm, b=1.3597（3） nm, c=0.8499（2） nm, V=1.1931（4） nm^3, Z=4, Dc=2.513 g/cm^3, R1=0.047 were obtained on the basis of 1365 reflections with Fo〉2σ（Fo）. PbN2O6 polyhedron adopts the distorted cubic configuration which is assigned to the holodirected geometry. These PbN2O6 polyhedra can form the zigzag chain by edge-sharing mode along（001） direction. Pb atom is connected by six nicotinic acid molecules, leading neutral 3D metal-organic framework with a channel defined by four Pb atoms and four nicotinic acid molecules.
文摘The development of novel porous materials have attracted significant attention owing to its possible application in several fields.In this study,we designed a novel covalent organic framework‐metal‐organic framework(COF‐MOF)material through an in‐situ ligand self‐assembly method.The in‐situ modified ligands not only act as nucleation sites to form Ti‐MOF,but also as a channel to rapidly transfer photogenerated electrons without introducing additional chemical bonds.The photocatalytic hydrogen production rate achieved over B‐CTF‐Ti‐MOF(1:1)was 1975μmol·g^(–1)·h^(–1) with an apparent quantum efficiency of 4.76%,which is 11.8 times higher than that of the pure CTF‐1.In addition,compared with the sample prepared by separating the ligands(CTF‐1/Ti‐MOF),B‐CTF‐Ti‐MOF shows excellent activity and stability.Finally,a reasonable photocatalytic mechanism was proposed using the results of electrochemical tests and spectral analyses.This study provides a universal method for the construction of highly efficient and stable COF/MOF materials with excellent properties.
