In this study,the ZIF-8 membrane(ZIF-8/PP-g-MAH)is prepared by in situ synthesis of ZIF-8 on irradiation-pretreated polymer substrates to improve the uranium adsorption performance and address the recycling problems o...In this study,the ZIF-8 membrane(ZIF-8/PP-g-MAH)is prepared by in situ synthesis of ZIF-8 on irradiation-pretreated polymer substrates to improve the uranium adsorption performance and address the recycling problems of ZIF-8 powder.The effects of pH,contact time,and uranium concentration on the adsorption of ZIF-8/PP-g-MAH were investigated.Adsorption isotherm and kinetics analysis show that ZIF-8/PP-g-MAH has a high adsorption capacity of 478.5 mg/g,which is 1.26 times higher than that of ZIF-8,and a rapid adsorption equilibrium of 120 min,which is shortened to one-third of that required for ZIF-8(360 min).The adsorption process of ZIF-8/PP-g-MAH is consistent with that of the Langmuir isotherm and pseudo-second-order dynamic model.ZIF-8/PP-g-MAH also exhibits good selectivity for uranium in simulated seawater.The high adsorption performance of ZIF-8/PP-g-MAH is attributed to its membrane structure,which improves the utilization of coordination sites,including Zn-OH,C-N,and C=N.This study provides an efficient adsorption material for rapid uranium extraction,thus promoting the development of uranium extraction technologies.展开更多
Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membra...Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.展开更多
Metal-organic frameworks(MOFs)have gained attention in the development of MOFs/polymer hybrid membranes for pervaporation.However,the agglomeration of MOFs particles and interfacial defects limit its further applicati...Metal-organic frameworks(MOFs)have gained attention in the development of MOFs/polymer hybrid membranes for pervaporation.However,the agglomeration of MOFs particles and interfacial defects limit its further application.In this study,we present a novel approach to fabricate a ZIF-8@PEBAX/PVDF nanocomposite membrane for removing thiophene from the model gasoline by combination of selfassembly and in-situ growth.Firstly,a PVDF supporting membrane was modified to have a negative charge.Next,positively charged zinc ions were attracted onto the negatively charged PVDF supporting membrane through electrostatic interaction.Afterwards,the Zinc ions deposited PVDF membrane was immersed into dimethylimidazole solution to form a uniform ZIF-8 layer.Finally,the ZIF-8 layer was coated with poly(ether-block-amide)(PEBAX)using the pouring method.Experimental results showed that the separating efficiency of the ZIF-8@PEBAX/PVDF nanocomposite membrane was improved significantly compared to that of pristine PEBAX membrane.The optimal permeation flux and enrichment factor of membrane were 27.80 kg(m^(2)h)^(-1)and 6.9,respectively.展开更多
Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher per...Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers.However,the selectivities of the reported membranes are moderate.Here,we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance.The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density.They can be well-dispersed in the organosilica layer,which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica,which is beneficial for improving the selectivity of membranes for gas separation.The results have shown that the enhanced ideal selectivity of H_(2)/CH_(4) was 165 and that of CO_(2)/CH_(4) was 43,with H_(2) permeance of about 1.25×10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) and CO_(2) permeance of 3.27×10^(−7) mol·m^(−2)·s^(−1)·Pa^(−1) at 0.2 MPa and 25℃.In conclusion,the high level of hybrid membranes can be used to separate H_(2)(or CO_(2))from the binary gas mixture H_(2)/CH_(4)(or CO_(2)/CH_(4)),which is important for gas separation in practical applications.Moreover,the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.展开更多
CO_(2)separation performance of polymer membranes can be significantly enhanced by selecting porous fillers with high CO_(2)affinity.Ionic liquids incorporation has been recognized as an effective strategy for improvi...CO_(2)separation performance of polymer membranes can be significantly enhanced by selecting porous fillers with high CO_(2)affinity.Ionic liquids incorporation has been recognized as an effective strategy for improving the separation ability of pristine porous fillers.However,the influence of the specific functional groups of ILs in IL@MOF composites on separation performance of MMMs still remains unclear.Herein,we designed three microenvironment-tuned IL@ZIF-8 composites in which the three ILs contain different functional groups(-CH3,–SO3H,and–NH2).Molecular simulation results showed that the NH2-IL@ZIF-8 has a commendable CO_(2)adsorption capacity and CO_(2)/CH4 adsorptive selectivity,and the results were well confirmed by the following experimental data.More importantly,the prepared NH2-IL@ZIF-8 based MMMs also exhibit superior CO_(2)separation performance among the three IL@ZIF-8 based MMMs owning to its high CO_(2)affinity.Thus,this work can provide guidance for designing IL@MOF composites for MMMs fabrication towards gas separation,and the research mode combining molecular simulation prediction and experimental verification can afford valuable reference for material development in membrane separation field.展开更多
文摘In this study,the ZIF-8 membrane(ZIF-8/PP-g-MAH)is prepared by in situ synthesis of ZIF-8 on irradiation-pretreated polymer substrates to improve the uranium adsorption performance and address the recycling problems of ZIF-8 powder.The effects of pH,contact time,and uranium concentration on the adsorption of ZIF-8/PP-g-MAH were investigated.Adsorption isotherm and kinetics analysis show that ZIF-8/PP-g-MAH has a high adsorption capacity of 478.5 mg/g,which is 1.26 times higher than that of ZIF-8,and a rapid adsorption equilibrium of 120 min,which is shortened to one-third of that required for ZIF-8(360 min).The adsorption process of ZIF-8/PP-g-MAH is consistent with that of the Langmuir isotherm and pseudo-second-order dynamic model.ZIF-8/PP-g-MAH also exhibits good selectivity for uranium in simulated seawater.The high adsorption performance of ZIF-8/PP-g-MAH is attributed to its membrane structure,which improves the utilization of coordination sites,including Zn-OH,C-N,and C=N.This study provides an efficient adsorption material for rapid uranium extraction,thus promoting the development of uranium extraction technologies.
基金supported by the National Natural Science Foundation of China (21978253)the Fundamental Research Funds for the Central Universities (226-2022-00020, 226-2022-00055)。
文摘Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.
基金the National Natural Science Foundation of China(22271022)Hubei Three Gorges Laboratory(SK212001).
文摘Metal-organic frameworks(MOFs)have gained attention in the development of MOFs/polymer hybrid membranes for pervaporation.However,the agglomeration of MOFs particles and interfacial defects limit its further application.In this study,we present a novel approach to fabricate a ZIF-8@PEBAX/PVDF nanocomposite membrane for removing thiophene from the model gasoline by combination of selfassembly and in-situ growth.Firstly,a PVDF supporting membrane was modified to have a negative charge.Next,positively charged zinc ions were attracted onto the negatively charged PVDF supporting membrane through electrostatic interaction.Afterwards,the Zinc ions deposited PVDF membrane was immersed into dimethylimidazole solution to form a uniform ZIF-8 layer.Finally,the ZIF-8 layer was coated with poly(ether-block-amide)(PEBAX)using the pouring method.Experimental results showed that the separating efficiency of the ZIF-8@PEBAX/PVDF nanocomposite membrane was improved significantly compared to that of pristine PEBAX membrane.The optimal permeation flux and enrichment factor of membrane were 27.80 kg(m^(2)h)^(-1)and 6.9,respectively.
基金supports of this work from“Pioneer”and“Leading Goose”R&D Program of Zhejiang Province(Grant No.2022C01029)National Natural Science Foundation of China(Grant No.21978309)+3 种基金Natural Science Foundation of Zhejiang Province(Grant No.LY21E020008)Youth Innovation Promotion Association,Chinese Acadenry of Sciences(Grant No.2020300)Ningbo Natural Science Foundation(Grant No.2023J354)Ningbo S&T Innovation 2025 Major Special Program(Grant No.2020Z036).
文摘Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers.However,the selectivities of the reported membranes are moderate.Here,we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance.The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density.They can be well-dispersed in the organosilica layer,which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica,which is beneficial for improving the selectivity of membranes for gas separation.The results have shown that the enhanced ideal selectivity of H_(2)/CH_(4) was 165 and that of CO_(2)/CH_(4) was 43,with H_(2) permeance of about 1.25×10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) and CO_(2) permeance of 3.27×10^(−7) mol·m^(−2)·s^(−1)·Pa^(−1) at 0.2 MPa and 25℃.In conclusion,the high level of hybrid membranes can be used to separate H_(2)(or CO_(2))from the binary gas mixture H_(2)/CH_(4)(or CO_(2)/CH_(4)),which is important for gas separation in practical applications.Moreover,the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.
基金the Natural Science Foundation of China(Nos.21536001,21878229 and 21978212)National Key Projects for Fundamental Research and Development of China(No.2016YFB0600901)the Science and Technology Plans of Tianjin(Nos.18PTSYJC00180 and 19PTSYJC00020).
文摘CO_(2)separation performance of polymer membranes can be significantly enhanced by selecting porous fillers with high CO_(2)affinity.Ionic liquids incorporation has been recognized as an effective strategy for improving the separation ability of pristine porous fillers.However,the influence of the specific functional groups of ILs in IL@MOF composites on separation performance of MMMs still remains unclear.Herein,we designed three microenvironment-tuned IL@ZIF-8 composites in which the three ILs contain different functional groups(-CH3,–SO3H,and–NH2).Molecular simulation results showed that the NH2-IL@ZIF-8 has a commendable CO_(2)adsorption capacity and CO_(2)/CH4 adsorptive selectivity,and the results were well confirmed by the following experimental data.More importantly,the prepared NH2-IL@ZIF-8 based MMMs also exhibit superior CO_(2)separation performance among the three IL@ZIF-8 based MMMs owning to its high CO_(2)affinity.Thus,this work can provide guidance for designing IL@MOF composites for MMMs fabrication towards gas separation,and the research mode combining molecular simulation prediction and experimental verification can afford valuable reference for material development in membrane separation field.