Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and act...Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and activated MIL-101(Fe))were synthesized and added to PEO-based solid composite electrolytes(SCEs).Furthermore,the role of the—NH_(2)groups and open metal sites(OMSs)were both examined.Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations.At last,we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO,Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries.This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.展开更多
Mesoporous materials with uniform pores and high specific areas are used in many fields including catalysts, separation and adsorbents, etc. In order to find faster and more economical synthesis routes, the use of mic...Mesoporous materials with uniform pores and high specific areas are used in many fields including catalysts, separation and adsorbents, etc. In order to find faster and more economical synthesis routes, the use of microwave heating was deeply studied. Compared to the hydrothermal method, microwave energy can heat the samples to crystallization temperature rapidly and uniformly result in homogeneous nucleation and shorten crystallization time. The basic principles of microwave assisted synthesis and advantages of microwave heating, and the obtained progress concerning ordered mesoporous materials through microwave synthesis were summarized.展开更多
Four stable MOF-74 analogues,namely Ni_(2)(dobdc),Ni_(2)(dobpdc),Ni_(2)(olz)and Ni_(2)(dotpdc),possessing abundant open metal sites(OMSs)and honeycomb channels with pore sizes ranging from 1.0 to_(2).6 nm,were used to...Four stable MOF-74 analogues,namely Ni_(2)(dobdc),Ni_(2)(dobpdc),Ni_(2)(olz)and Ni_(2)(dotpdc),possessing abundant open metal sites(OMSs)and honeycomb channels with pore sizes ranging from 1.0 to_(2).6 nm,were used to research the effects of the pore size on D_(2)/H_(2)separation from the hydrogen isotope mixture through dynamic column breakthrough experiments.展开更多
In the activation process of MOF materials,the formation of open metal sites(OMSs)generally enhances the binding force between the framework and C_(2)H_(2)/C_(2)H_(4),while it can also lead to co-adsorption and signif...In the activation process of MOF materials,the formation of open metal sites(OMSs)generally enhances the binding force between the framework and C_(2)H_(2)/C_(2)H_(4),while it can also lead to co-adsorption and significantly reduce separation efficiency.In actual working environments,OMSs are susceptible to water attacks,rendering the material more prone to damage.Herein,a heptanuclear cluster-based MOF material denoted as Ni7-MOF is reported,which is constructed using extremely inexpensive organic linkers under pure water conditions.Two vip-free materials,Ni7-100 with coordinated water and Ni7-250 with OMSs,were obtained to investigate the C_(2)H_(2)/C_(2)H_(4) separation properties and mechanisms.The enhanced adsorption and separation performance of Ni7-250 compared to Ni7-100 is primarily attributed to the appropriate pore environment within the framework,leading to the dense packing of vip molecules,and is independent of OMSs.This conclusion is further supported by grand canonical Monte Carlo(GCMC)calculations.Due to the stability of nickel ions in the pentagonal pyramid structure,Ni7-250 with OMSs exhibits high stability and can achieve structural restoration under water vapor conditions.Although environmental factors can disrupt MOF materials through OMSs,such disruption can be avoided by selecting metal ions for MOF materials based on the stability of metal ion coordination geometry.Concurrently,the regeneration of materials through the adsorption of water vapor by OMSs in the air can achieve a longer service life.展开更多
A polyhedral metal-organic framework(MOF)JLU-Liu40-In based on dual secondary building units(SBUs)of mononuclear and binuclear paddlewheel indium has been prepared with a nitrogen-rich tetracarboxylic acid ligand unde...A polyhedral metal-organic framework(MOF)JLU-Liu40-In based on dual secondary building units(SBUs)of mononuclear and binuclear paddlewheel indium has been prepared with a nitrogen-rich tetracarboxylic acid ligand under solvothermal conditions.Since the framework possesses large surface areas with multiple polyhedral cages,abundant open metal sites(OMSs)and Lewis basic sites(LBSs),it exhibits high performance for gas adsorption.In addition,through post-synthetic metal-ion metathesis in a single-crystal-to-single-crystal(SCSC)process,JLU-Liu40-In/Cu has been obtained by selectively substituting the paddlewheel In(Ⅲ)ions with Cu(Ⅱ)ions without replacing the mononuclear In(Ⅲ).The framework remains in the form of a single crystal throughout the process.It is worth noting that the metal-ion metathesis approach constructs JLU-Liu40-In/Cu with a significant improvement in thermal stability and gas sorption and separation.展开更多
Water induced decomposition of Cu3（BTC）2 （BTC= benzene-l,3,5-tricarboxylate） metal-organic framework （MOF） was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infra...Water induced decomposition of Cu3（BTC）2 （BTC= benzene-l,3,5-tricarboxylate） metal-organic framework （MOF） was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infrared spectroscopy and differential scanning calorimetry analyses revealed that the underlying mechanism of Cu3（BTC）2 MOF decomposition under humid streams is the interpenetration of water molecules into Cu-BTC coordination to displace organic linkers （BTC） from Cu centres.展开更多
基金financially supported by National Natural Science Foundation of China(21701083)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_3137)。
文摘Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and activated MIL-101(Fe))were synthesized and added to PEO-based solid composite electrolytes(SCEs).Furthermore,the role of the—NH_(2)groups and open metal sites(OMSs)were both examined.Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations.At last,we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO,Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries.This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.
基金Project(20775096/B050104) supported by the National Natural Science Foundation of ChinaProject(20080440696) supported by China Postdoctoral Science Foundation
文摘Mesoporous materials with uniform pores and high specific areas are used in many fields including catalysts, separation and adsorbents, etc. In order to find faster and more economical synthesis routes, the use of microwave heating was deeply studied. Compared to the hydrothermal method, microwave energy can heat the samples to crystallization temperature rapidly and uniformly result in homogeneous nucleation and shorten crystallization time. The basic principles of microwave assisted synthesis and advantages of microwave heating, and the obtained progress concerning ordered mesoporous materials through microwave synthesis were summarized.
基金financially supported by the Key Research Program of Frontier Sciences,by the CAS(QYZDB-SSW-SLH019)by the National Natural Science Foundation of China(21771177).
文摘Four stable MOF-74 analogues,namely Ni_(2)(dobdc),Ni_(2)(dobpdc),Ni_(2)(olz)and Ni_(2)(dotpdc),possessing abundant open metal sites(OMSs)and honeycomb channels with pore sizes ranging from 1.0 to_(2).6 nm,were used to research the effects of the pore size on D_(2)/H_(2)separation from the hydrogen isotope mixture through dynamic column breakthrough experiments.
基金the Natural Science Foundation of Ningbo(2022J101)support of the Shanghai Synchrotron Radiation Facility,instrument BL17B.
文摘In the activation process of MOF materials,the formation of open metal sites(OMSs)generally enhances the binding force between the framework and C_(2)H_(2)/C_(2)H_(4),while it can also lead to co-adsorption and significantly reduce separation efficiency.In actual working environments,OMSs are susceptible to water attacks,rendering the material more prone to damage.Herein,a heptanuclear cluster-based MOF material denoted as Ni7-MOF is reported,which is constructed using extremely inexpensive organic linkers under pure water conditions.Two vip-free materials,Ni7-100 with coordinated water and Ni7-250 with OMSs,were obtained to investigate the C_(2)H_(2)/C_(2)H_(4) separation properties and mechanisms.The enhanced adsorption and separation performance of Ni7-250 compared to Ni7-100 is primarily attributed to the appropriate pore environment within the framework,leading to the dense packing of vip molecules,and is independent of OMSs.This conclusion is further supported by grand canonical Monte Carlo(GCMC)calculations.Due to the stability of nickel ions in the pentagonal pyramid structure,Ni7-250 with OMSs exhibits high stability and can achieve structural restoration under water vapor conditions.Although environmental factors can disrupt MOF materials through OMSs,such disruption can be avoided by selecting metal ions for MOF materials based on the stability of metal ion coordination geometry.Concurrently,the regeneration of materials through the adsorption of water vapor by OMSs in the air can achieve a longer service life.
基金financial support from the National Natural Science Foundation of China(No.21771078 and 21621001)the 111 Project(B17020)+2 种基金the National Key Research and Development Program of China(2016YFB0701100)the Fundamental Research Funds for the Central Universities of Ocean University of China(201813031)the Shandong Province Natural Foundation of China(ZR2019BB033).
文摘A polyhedral metal-organic framework(MOF)JLU-Liu40-In based on dual secondary building units(SBUs)of mononuclear and binuclear paddlewheel indium has been prepared with a nitrogen-rich tetracarboxylic acid ligand under solvothermal conditions.Since the framework possesses large surface areas with multiple polyhedral cages,abundant open metal sites(OMSs)and Lewis basic sites(LBSs),it exhibits high performance for gas adsorption.In addition,through post-synthetic metal-ion metathesis in a single-crystal-to-single-crystal(SCSC)process,JLU-Liu40-In/Cu has been obtained by selectively substituting the paddlewheel In(Ⅲ)ions with Cu(Ⅱ)ions without replacing the mononuclear In(Ⅲ).The framework remains in the form of a single crystal throughout the process.It is worth noting that the metal-ion metathesis approach constructs JLU-Liu40-In/Cu with a significant improvement in thermal stability and gas sorption and separation.
文摘Water induced decomposition of Cu3（BTC）2 （BTC= benzene-l,3,5-tricarboxylate） metal-organic framework （MOF） was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infrared spectroscopy and differential scanning calorimetry analyses revealed that the underlying mechanism of Cu3（BTC）2 MOF decomposition under humid streams is the interpenetration of water molecules into Cu-BTC coordination to displace organic linkers （BTC） from Cu centres.
