Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fund...Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.展开更多
CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organ...CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.展开更多
This paper analyzed the problems in the existing framework, and achieved a reasonable framework based on reflection and aspect-oriented programming combined with annotations to map the request parameters, and inversio...This paper analyzed the problems in the existing framework, and achieved a reasonable framework based on reflection and aspect-oriented programming combined with annotations to map the request parameters, and inversion of the control of the various components. The proposed framework reduced the volume of the application context, and achieved the purpose that dependencies between the various components are controlled by the framework. Based on the problems existing in the known framework, the lightweight MVC framework was implemented and the proposed framework was tested by JMeter test tool. The test results showed that the framework proposed in this paper can respond to requests faster, improve access throughput and enhance application performance and user experience. The framework proposed in this paper combined the functions of MVC and IOC to minimize the volume of external dependencies in the development and greatly improved the efficiency of Web applications development.展开更多
(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to it...Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.展开更多
The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic ...The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.展开更多
Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreo...Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreover,due to the accumulation of COFs nanoparticles,it is not conducive to the full utilization of their surface functional groups.Currently,the strategy of COFs assembling into aerogel can be a good solution to this problem.Herein,we successfully synthesize composite aerogels(CSR)by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate.Sodium alginate in the composite improves the mechanical properties of the aerogel,and graphene provides a template for the in-situ growth of COFs.Impressively,CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs.The prepared CSR aerogels exhibit porous,low density,good processability and good mechanical properties.Among them,the density of CSR-N-1.6 is only 5 mg/cm3,which is the lowest density among the reported COF aerogels so far.Due to these remarkable properties,CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants(organic dyes and antibiotics)from polluted water.In addition,it is also possible to visually recognize the presence of antibiotics by fluorescence detection.This work not only provides a new strategy for synthesizing COF aerogels,but also accelerates the practical application of COF aerogels and contributes to environmental remediation.展开更多
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
基金supported by National Natural Science Foundation of China(32494793).
文摘Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.
文摘CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.
文摘This paper analyzed the problems in the existing framework, and achieved a reasonable framework based on reflection and aspect-oriented programming combined with annotations to map the request parameters, and inversion of the control of the various components. The proposed framework reduced the volume of the application context, and achieved the purpose that dependencies between the various components are controlled by the framework. Based on the problems existing in the known framework, the lightweight MVC framework was implemented and the proposed framework was tested by JMeter test tool. The test results showed that the framework proposed in this paper can respond to requests faster, improve access throughput and enhance application performance and user experience. The framework proposed in this paper combined the functions of MVC and IOC to minimize the volume of external dependencies in the development and greatly improved the efficiency of Web applications development.
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
基金supported by the National Natural Science Foundation of China(Nos.52373280,52177014 and 52273257).
文摘Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.
基金supported by the Natural Science Research Project of the Anhui Educational Committee,China(No.2022AH050827)the Open Research Fund Program of Anhui Province Key Laboratory of Specialty Polymers,Anhui University of Science and Technology,China(No.AHKLSP23-12)the Joint National-Local Engineering Research Center for Safe and Precise Coal Mining Fund,China(No.EC2022020)。
文摘The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.
基金the financial support provided by the National Natural Science Foundation of China(Nos.22175094,21971113)。
文摘Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreover,due to the accumulation of COFs nanoparticles,it is not conducive to the full utilization of their surface functional groups.Currently,the strategy of COFs assembling into aerogel can be a good solution to this problem.Herein,we successfully synthesize composite aerogels(CSR)by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate.Sodium alginate in the composite improves the mechanical properties of the aerogel,and graphene provides a template for the in-situ growth of COFs.Impressively,CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs.The prepared CSR aerogels exhibit porous,low density,good processability and good mechanical properties.Among them,the density of CSR-N-1.6 is only 5 mg/cm3,which is the lowest density among the reported COF aerogels so far.Due to these remarkable properties,CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants(organic dyes and antibiotics)from polluted water.In addition,it is also possible to visually recognize the presence of antibiotics by fluorescence detection.This work not only provides a new strategy for synthesizing COF aerogels,but also accelerates the practical application of COF aerogels and contributes to environmental remediation.
