Zeolitic imidazole frameworks(ZIFs)are a class of three-dimensional(3D)skeletalmaterials with zeolitic topology composed of metal ions and imidazolium ligands,which combine the advantages of zeolites and metal-organic...Zeolitic imidazole frameworks(ZIFs)are a class of three-dimensional(3D)skeletalmaterials with zeolitic topology composed of metal ions and imidazolium ligands,which combine the advantages of zeolites and metal-organic frameworks.ZIFs are widely used for adsorption of carbon dioxide(CO_(2))from flue gas due to its excellent hydrophobicity,chemical stability,thermal stability and gas adsorption properties.This study focuses on the effects of structures of ZIFs on CO_(2)capture and separation from the viewpoints of topologies,pore channels,ligand functional groups and composite structures.On this basis,the mechanisms of CO_(2)adsorption and selective separation are reviewed,as well as the challenges such as hydrophobicity,thermal and chemical stability faced by ZIFs in practical applications.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
Peracetic acid(PAA)-based system is becoming an emerging advanced oxidation process(AOP)for effective removal of organic contaminants from water.Various approaches have been tested to activate PAA,while no previous re...Peracetic acid(PAA)-based system is becoming an emerging advanced oxidation process(AOP)for effective removal of organic contaminants from water.Various approaches have been tested to activate PAA,while no previous researches reported the application of metal-organic frameworks(MOFs)materials for PAA activation.In this study,zeolitic imidazole framework(ZIF)-67,a representative MOFs,was facile synthesized via direct-mixing method at room temperature,and tested for PAA activation and sulfachloropyridazine(SCP)degradation.The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100%of SCP degraded within 3 min,owing to the specific MOFs structure and abundant Co^(2+) sites.The pseudo-first-order kinetic model was applied to fit the kinetic data,with rate constant k_(1) of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co_(3)O_(4)activated PAA and direct oxidation by PAA.Radical quenching experiments and electron paramagnetic resonance(EPR)analysis indicated that CH_(3)C(O)OO^(·)played a major role in this PAA activation system.Then,the Fukui index based on density functional theory(DFT)calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH_(3)C(O)OO^(·).In addition,the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection,which mainly included the S-N bond cleavage and SO_(2)extrusion and followed by further oxidation,dechlorination,and hydroxylation.Therefore,ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants(EOCs)from water.展开更多
针对印染废水难以处理而对环境造成污染问题,以活性黑染料为目标污染物,制备了一种ZIF-8/MCM-48新型复合吸附材料,并采用X射线衍射(X-ray Diffraction,XRD)、扫描电镜(Scanning Electron Microscopy,SEM)、N_(2)的吸脱附曲线对其形貌、...针对印染废水难以处理而对环境造成污染问题,以活性黑染料为目标污染物,制备了一种ZIF-8/MCM-48新型复合吸附材料,并采用X射线衍射(X-ray Diffraction,XRD)、扫描电镜(Scanning Electron Microscopy,SEM)、N_(2)的吸脱附曲线对其形貌、结构、组成进行表征,研究了其对活性黑染料废水的吸附性能,并通过调整ZIF-8/MCM-48复合物比例、活性黑染料废水浓度、染料废水pH值及吸附时间,来确定最大吸附量和最佳吸附条件。结果表明,ZIF-8/MCM-48复合吸附剂的投加量为0.4 g/L、废水pH值为6、吸附时间为50 min时,0.15 g/L活性黑染料废水的脱色率达到了最高,为58.7%。最后对吸附过程进行了动力学分析,发现其符合二级动力学方程。展开更多
Traditional methods of preparing metal-organic frameworks(MOFs)compounds have the disadvantages such as poor dispersion,inefficient and discontinuous process.In this work,microchannel reactor is used to prepare MOFs-d...Traditional methods of preparing metal-organic frameworks(MOFs)compounds have the disadvantages such as poor dispersion,inefficient and discontinuous process.In this work,microchannel reactor is used to prepare MOFs-derived zeolite-imidazole material via flash nanoprecipitation to form ZIF-67+PEI(FNP),which reduces the MOF synthesis time down to millisecond time interval while keeping the synthesized ZIF-67+PEI(FNP)highly dispersed.The Co@N–C(FNP)catalyst obtained by flash nanoprecipitation and carbonization has a higher Co content and thus more active sites for oxygen reduction reaction than the Co@N–C(DM)catalyst prepared by direct mixing method.Electrochemical tests show that the Co@N–C(FNP)catalyst prepared by this method has excellent oxygen reduction performance,good methanol resistance and high stability.The onset potential and half-wave potential of Co@N–C(FNP)are 0.92 VRHE and 0.83 VRHE,respectively,which are higher than that of Co@N–C(DM)(Eonset=0.90 VRHEand E1/2=0.83VRHE).Moreover,the Zn-air battery assembled with Co@N–C(FNP)as the cathode catalyst has high open circuit voltage,high power density and large specific capacity.The performance of these batteries has been comparable to that of Pt/C assembled batteries.Density functional theory(DFT)calculations confirm that the Co(220)crystal plane present in Co@N–C(FNP)have stronger adsorption energy than that of Co(111)crystal plane in Co@N–C(DM),leading to better electrocatalytic performance of the former.展开更多
Carbon super-heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks(CTFs)and zeolitic imidazolic frameworks(ZIFs)are scarcely explored because of CTF's ord...Carbon super-heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks(CTFs)and zeolitic imidazolic frameworks(ZIFs)are scarcely explored because of CTF's ordered structure and toxic superacid that dissolves or destabilizes the metal nodes.To solve this problem,herein,we report a straightforward two-step pathway for the covalent hybridization of disordered CTF(d–CTF)–ZIF composites via preincorporation of an imidazole(IM)linker into ordered CTFs,followed by the imidazole-site-specific covalent growth of ZIFs.Direct carbonization of these synthesized d–CTF−IM−ZIF hybrids results in unique hollow carbon super-heterostructures with ultrahigh nitrogen content(>18.6%),high specific surface area(1663m^(2)g^(−1)),and beneficial trace metal(Co/Zn NPs)contents for promoting the redox pseudocapacitance.As proof of concept,the obtained carbon super-heterostructure(Co–Zn–NC_(SNH)–800)is used as a positive electrode in an asymmetric supercapacitor,demonstrating a remarkable energy density of 61Wh kg^(−1)and extraordinary cyclic stability of 97%retention after 30,000 cycles at the cell level.Our presynthetic modifications of CTF and their covalent hybridization with ZIF crystals pave the way toward new design strategies for synthesizing functional porous carbon materials for promising energy applications.展开更多
基金supported by the Fundamental Research Program of Shanxi Province(Nos.20210302124003 and 20210302124015)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No.2021L032)+2 种基金the National Natural Science Foundation of China(No.52103307)China Postdoctoral Science Foundation(No.2023M742575)the General Program of Shanxi Province(No.202203021211150).
文摘Zeolitic imidazole frameworks(ZIFs)are a class of three-dimensional(3D)skeletalmaterials with zeolitic topology composed of metal ions and imidazolium ligands,which combine the advantages of zeolites and metal-organic frameworks.ZIFs are widely used for adsorption of carbon dioxide(CO_(2))from flue gas due to its excellent hydrophobicity,chemical stability,thermal stability and gas adsorption properties.This study focuses on the effects of structures of ZIFs on CO_(2)capture and separation from the viewpoints of topologies,pore channels,ligand functional groups and composite structures.On this basis,the mechanisms of CO_(2)adsorption and selective separation are reviewed,as well as the challenges such as hydrophobicity,thermal and chemical stability faced by ZIFs in practical applications.
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.
基金the National Natural Science Foundation of China(Nos.21906001 and 52100069)the National Key Research and Development Program of China(No.2021YFA1202500)+2 种基金Beijing Nova Program(No.Z191100001119054)the Fundamental Research Funds for the Central Universities(No.BFUKF202118)China Postdoctoral Science Foundation(No.2021M690208)。
文摘Peracetic acid(PAA)-based system is becoming an emerging advanced oxidation process(AOP)for effective removal of organic contaminants from water.Various approaches have been tested to activate PAA,while no previous researches reported the application of metal-organic frameworks(MOFs)materials for PAA activation.In this study,zeolitic imidazole framework(ZIF)-67,a representative MOFs,was facile synthesized via direct-mixing method at room temperature,and tested for PAA activation and sulfachloropyridazine(SCP)degradation.The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100%of SCP degraded within 3 min,owing to the specific MOFs structure and abundant Co^(2+) sites.The pseudo-first-order kinetic model was applied to fit the kinetic data,with rate constant k_(1) of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co_(3)O_(4)activated PAA and direct oxidation by PAA.Radical quenching experiments and electron paramagnetic resonance(EPR)analysis indicated that CH_(3)C(O)OO^(·)played a major role in this PAA activation system.Then,the Fukui index based on density functional theory(DFT)calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH_(3)C(O)OO^(·).In addition,the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection,which mainly included the S-N bond cleavage and SO_(2)extrusion and followed by further oxidation,dechlorination,and hydroxylation.Therefore,ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants(EOCs)from water.
基金supported by National Natural Science Foundation of China(No.21865025)Science and Technology Innovation Talents Program of Bingtuan(No.2019CB025)。
文摘Traditional methods of preparing metal-organic frameworks(MOFs)compounds have the disadvantages such as poor dispersion,inefficient and discontinuous process.In this work,microchannel reactor is used to prepare MOFs-derived zeolite-imidazole material via flash nanoprecipitation to form ZIF-67+PEI(FNP),which reduces the MOF synthesis time down to millisecond time interval while keeping the synthesized ZIF-67+PEI(FNP)highly dispersed.The Co@N–C(FNP)catalyst obtained by flash nanoprecipitation and carbonization has a higher Co content and thus more active sites for oxygen reduction reaction than the Co@N–C(DM)catalyst prepared by direct mixing method.Electrochemical tests show that the Co@N–C(FNP)catalyst prepared by this method has excellent oxygen reduction performance,good methanol resistance and high stability.The onset potential and half-wave potential of Co@N–C(FNP)are 0.92 VRHE and 0.83 VRHE,respectively,which are higher than that of Co@N–C(DM)(Eonset=0.90 VRHEand E1/2=0.83VRHE).Moreover,the Zn-air battery assembled with Co@N–C(FNP)as the cathode catalyst has high open circuit voltage,high power density and large specific capacity.The performance of these batteries has been comparable to that of Pt/C assembled batteries.Density functional theory(DFT)calculations confirm that the Co(220)crystal plane present in Co@N–C(FNP)have stronger adsorption energy than that of Co(111)crystal plane in Co@N–C(DM),leading to better electrocatalytic performance of the former.
基金Ministry of Trade,Industry&Energy of Korea,Grant/Award Number:RS‐2022‐00155717National Research Foundation of Korea,Grant/Award Numbers:2020H1D3A1A04081472,2022M3J1A1054323。
文摘Carbon super-heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks(CTFs)and zeolitic imidazolic frameworks(ZIFs)are scarcely explored because of CTF's ordered structure and toxic superacid that dissolves or destabilizes the metal nodes.To solve this problem,herein,we report a straightforward two-step pathway for the covalent hybridization of disordered CTF(d–CTF)–ZIF composites via preincorporation of an imidazole(IM)linker into ordered CTFs,followed by the imidazole-site-specific covalent growth of ZIFs.Direct carbonization of these synthesized d–CTF−IM−ZIF hybrids results in unique hollow carbon super-heterostructures with ultrahigh nitrogen content(>18.6%),high specific surface area(1663m^(2)g^(−1)),and beneficial trace metal(Co/Zn NPs)contents for promoting the redox pseudocapacitance.As proof of concept,the obtained carbon super-heterostructure(Co–Zn–NC_(SNH)–800)is used as a positive electrode in an asymmetric supercapacitor,demonstrating a remarkable energy density of 61Wh kg^(−1)and extraordinary cyclic stability of 97%retention after 30,000 cycles at the cell level.Our presynthetic modifications of CTF and their covalent hybridization with ZIF crystals pave the way toward new design strategies for synthesizing functional porous carbon materials for promising energy applications.
