Pub Date : 2025-04-04DOI: 10.1016/j.memsci.2025.124069
Yanchuan Zhang, Yali Zhao, Yu Liu
Loose nanofiltration (NF) membranes are promising in textile wastewater treatment due to their selective separation capabilities for dyes and salts. However, their widespread applications are hindered by complex manufacturing processes and membrane fouling. This work focuses on fabricating antifouling loose NF membranes using a facile method. Thereinto, amine-functionalized loose NF matrixes were first prepared using polyelectrolyte-complex induced phase inversion, where polyethyleneimine (PEI) in a coagulation bath as an inducer triggered an instantaneous phase inversion via electrostatic interactions with sulfonated polysulfone (SPSF) in dope solution. The acquired NF matrix has a dense skin layer with a mean pore size of 0.72 nm, endowing it with excellent dye retention. Consequently, the Fenton catalyst, MnO2, was in situ grown on the membrane via the interaction between amine and Mn2+ followed by a one-step mineralization reaction. The MnO2-loaded loose NF membrane could achieve 99.7 % CR rejection while allowing only 1.67 % rejection of Na2SO4 in a mixed solution of 60 mg/L Congo Red (CR) and 20 g/L Na2SO4 at the permeability of 51.6 L m−2 h−1·bar−1. After cleaning with H2O2, the flux recovery rate of the membrane remains above 97 %, attributed to the catalytic effect of MnO2 on the membrane surface. Additionally, the membrane displayed similar performance in dealing with real wastewater, underscoring its potential for practical applications in textile wastewater treatment.
{"title":"Highly efficient MnO2-modified antifouling loose nanofiltration membrane for dye/salt separation","authors":"Yanchuan Zhang, Yali Zhao, Yu Liu","doi":"10.1016/j.memsci.2025.124069","DOIUrl":"10.1016/j.memsci.2025.124069","url":null,"abstract":"<div><div>Loose nanofiltration (NF) membranes are promising in textile wastewater treatment due to their selective separation capabilities for dyes and salts. However, their widespread applications are hindered by complex manufacturing processes and membrane fouling. This work focuses on fabricating antifouling loose NF membranes using a facile method. Thereinto, amine-functionalized loose NF matrixes were first prepared using polyelectrolyte-complex induced phase inversion, where polyethyleneimine (PEI) in a coagulation bath as an inducer triggered an instantaneous phase inversion via electrostatic interactions with sulfonated polysulfone (SPSF) in dope solution. The acquired NF matrix has a dense skin layer with a mean pore size of 0.72 nm, endowing it with excellent dye retention. Consequently, the Fenton catalyst, MnO<sub>2</sub>, was in situ grown on the membrane via the interaction between amine and Mn<sup>2+</sup> followed by a one-step mineralization reaction. The MnO<sub>2</sub>-loaded loose NF membrane could achieve 99.7 % CR rejection while allowing only 1.67 % rejection of Na<sub>2</sub>SO<sub>4</sub> in a mixed solution of 60 mg/L Congo Red (CR) and 20 g/L Na<sub>2</sub>SO<sub>4</sub> at the permeability of 51.6 L m<sup>−2</sup> h<sup>−1</sup>·bar<sup>−1</sup>. After cleaning with H<sub>2</sub>O<sub>2</sub>, the flux recovery rate of the membrane remains above 97 %, attributed to the catalytic effect of MnO<sub>2</sub> on the membrane surface. Additionally, the membrane displayed similar performance in dealing with real wastewater, underscoring its potential for practical applications in textile wastewater treatment.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124069"},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1016/j.memsci.2025.124024
Yuan Chen , Ziwei Sun , Zhen Xu , Hanlei Lin , Jun Gao , Jiongsheng Song , Zhenyu Li , Ronghai Huang , Yaping Geng , Dingsheng Wu , Quan Feng
Membrane separation technology has received extensive attention in water purification. However, in practical applications, separation membranes still face challenges like complex preparation processes, high filtration energy consumption, and low flux. Therefore, in this study, the scalable, high-throughput and highly durable PVA-based nanofiber separation membranes has been manufacture by employing needle-free electrospinning technology. Subsequently, PVA nanofiber membranes with double-bond addition cyclopolymerisation were prepared through photocrosslinking, and their performance in advanced water purification was explored. The results indicated that through facile graft modification and the needle-free electrospinning method, the scalable PVA-based nanofiber membranes with a diameter of 270 nm can be produced. The production efficiency is around 15 g/h, which is obviously higher than that of the existing electrospinning process.Under 0.05 MPa, the pure water flux of the PVA-based nanofiber membrane could be maintained at a maximum of 4785.23 L/(), and the interception rate was 99 % ( 10 nm). When filtering lake water, the results indicated that the permanganate index in the lake water was significantly reduced to 1.05 mg/L ( 3 mg/L), demonstrating excellent water purification performance. Importantly, the designed photocrosslinking is a convenient, low-energy and environmentally-friendly crosslinking process that can effectively control the degree of swelling of PVA nanofibers compared to traditional crosslinking techniques. Meanwhile, the process can effectively control the pore structure of PVA nanofiber membrane. This successfully solved the problems of easy dissolution and low filtration efficiency of PVA nanofiber membranes. This study opened up prospects for the efficient preparation of nanofiber separation membranes and their applications in water treatment.
{"title":"Scalable, high flux and durable electrospun photocrosslinked PVA nanofibers-based membrane for efficient water purification","authors":"Yuan Chen , Ziwei Sun , Zhen Xu , Hanlei Lin , Jun Gao , Jiongsheng Song , Zhenyu Li , Ronghai Huang , Yaping Geng , Dingsheng Wu , Quan Feng","doi":"10.1016/j.memsci.2025.124024","DOIUrl":"10.1016/j.memsci.2025.124024","url":null,"abstract":"<div><div>Membrane separation technology has received extensive attention in water purification. However, in practical applications, separation membranes still face challenges like complex preparation processes, high filtration energy consumption, and low flux. Therefore, in this study, the scalable, high-throughput and highly durable PVA-based nanofiber separation membranes has been manufacture by employing needle-free electrospinning technology. Subsequently, PVA nanofiber membranes with double-bond addition cyclopolymerisation were prepared through photocrosslinking, and their performance in advanced water purification was explored. The results indicated that through facile graft modification and the needle-free electrospinning method, the scalable PVA-based nanofiber membranes with a diameter of 270 nm can be produced. The production efficiency is around 15 g/h, which is obviously higher than that of the existing electrospinning process.Under 0.05 MPa, the pure water flux of the PVA-based nanofiber membrane could be maintained at a maximum of 4785.23 L/(<span><math><mrow><msup><mrow><mi>m</mi></mrow><mrow><mn>2</mn></mrow></msup><mspace></mspace><mi>h</mi></mrow></math></span>), and the interception rate was 99 % (<span><math><mo>⩾</mo></math></span> 10 nm). When filtering lake water, the results indicated that the permanganate index in the lake water was significantly reduced to 1.05 mg/L (<span><math><mo>⩽</mo></math></span> 3 mg/L), demonstrating excellent water purification performance. Importantly, the designed photocrosslinking is a convenient, low-energy and environmentally-friendly crosslinking process that can effectively control the degree of swelling of PVA nanofibers compared to traditional crosslinking techniques. Meanwhile, the process can effectively control the pore structure of PVA nanofiber membrane. This successfully solved the problems of easy dissolution and low filtration efficiency of PVA nanofiber membranes. This study opened up prospects for the efficient preparation of nanofiber separation membranes and their applications in water treatment.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"727 ","pages":"Article 124024"},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1016/j.memsci.2025.124068
Jinhuai Hua , Rui Yao , Haonan Xu , Wenbin Zhao , Yuping Zhou , Hua Jin , Yanshuo Li
This study addresses the challenges of bio-butanol recovery by synergizing innovative module design with advanced mixed matrix membranes (MMMs) for enhanced pervaporation (PV) efficiency. ZIF-8 nanoparticles (14–120 nm) were integrated into a polymethylphenylsiloxane (PMPS) matrix to fabricate ZIF-8/PMPS MMMs on flat-sheet Al2O3 supports, for efficient n-butanol separation via pervaporation. The optimized 14 nm-ZIF-8/PMPS MMMs (13.0 wt% loading) exhibited optimal performance, achieving a total flux of 925.86 g m−2 h−1 and a separation factor of 37.65 for 1 wt% n-butanol/water mixtures at 40 °C, enabling stable operation over 600 h. Key factors included the improved hydrophobicity, reduced interfacial voids, and enhanced surface roughness. A novel plate-and-frame module was engineered to address scalability challenges, increasing packing density from 5 to 55 m2/m3 while mitigating concentration polarization and enhancing mass transfer under dynamic flow conditions. The module's compact design, combined with the mechanical robustness of Al2O3 supports and the compatibility of ZIF-8/PMPS membranes, demonstrates industrial viability.
{"title":"A novel high-packing-density plate-and-frame membrane module integrated with ZIF-8/PMPS mixed matrix membranes for efficient butanol recovery from dilute solutions","authors":"Jinhuai Hua , Rui Yao , Haonan Xu , Wenbin Zhao , Yuping Zhou , Hua Jin , Yanshuo Li","doi":"10.1016/j.memsci.2025.124068","DOIUrl":"10.1016/j.memsci.2025.124068","url":null,"abstract":"<div><div>This study addresses the challenges of bio-butanol recovery by synergizing innovative module design with advanced mixed matrix membranes (MMMs) for enhanced pervaporation (PV) efficiency. ZIF-8 nanoparticles (14–120 nm) were integrated into a polymethylphenylsiloxane (PMPS) matrix to fabricate ZIF-8/PMPS MMMs on flat-sheet Al<sub>2</sub>O<sub>3</sub> supports, for efficient n-butanol separation via pervaporation. The optimized 14 nm-ZIF-8/PMPS MMMs (13.0 wt% loading) exhibited optimal performance, achieving a total flux of 925.86 g m<sup>−2</sup> h<sup>−1</sup> and a separation factor of 37.65 for 1 wt% n-butanol/water mixtures at 40 °C, enabling stable operation over 600 h. Key factors included the improved hydrophobicity, reduced interfacial voids, and enhanced surface roughness. A novel plate-and-frame module was engineered to address scalability challenges, increasing packing density from 5 to 55 m<sup>2</sup>/m<sup>3</sup> while mitigating concentration polarization and enhancing mass transfer under dynamic flow conditions. The module's compact design, combined with the mechanical robustness of Al<sub>2</sub>O<sub>3</sub> supports and the compatibility of ZIF-8/PMPS membranes, demonstrates industrial viability.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124068"},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.memsci.2025.124057
Xinyue Shang, Ruoman Ji, Lijuan Gao, Shuyi Li, Riji Qiu, Ting Wang
After modification of MOF-919 by bovine serum albumin (BSA) and further membrane formation, a novel metal-organic framework (MOF) chiral membrane based on protein functionalization was prepared. In the process, the stability of biomacromolecules under harsh conditions could be enormously raised on account of the combination MOF and BSA, while imparting chirality to the modified MOF. The influence of conditions such as reaction time, pH, initial concentration and salt concentration on the efficiency of MOF immobilized BSA were discussed. The outcomes indicated that the binding between MOF-919 and BSA was due to the synergistic interplay of pore diffusion and surface adsorption mechanisms. Meanwhile, after the immobilization, the composite material (MOF-919@BSA) was developed as a new kind of chiral splitter that combined with polyethersulfone to form the MMM. As well as the concentration of feed solution, thickness of membrane, proportion of biocomposite materials in membrane, the penetration time, cycle index and the micro environment of BSA on the separation of chiral enantiomers from the MMMs were investigated. The chiral membrane had excellent selectivity and high flux in the process of transporting chiral enantiomers. After that, the reliability of the mechanism for chiral separation was demonstrated through molecular docking simulations. At the same time, MOF@BSA-PES mixed matrix membrane manifested superior performance compared with the majority of state-of-the-art chiral membranes.
{"title":"Bovine serum albumin functional MOF-919 novel membranes for effective separation of chiral enantiomers","authors":"Xinyue Shang, Ruoman Ji, Lijuan Gao, Shuyi Li, Riji Qiu, Ting Wang","doi":"10.1016/j.memsci.2025.124057","DOIUrl":"10.1016/j.memsci.2025.124057","url":null,"abstract":"<div><div>After modification of MOF-919 by bovine serum albumin (BSA) and further membrane formation, a novel metal-organic framework (MOF) chiral membrane based on protein functionalization was prepared. In the process, the stability of biomacromolecules under harsh conditions could be enormously raised on account of the combination MOF and BSA, while imparting chirality to the modified MOF. The influence of conditions such as reaction time, pH, initial concentration and salt concentration on the efficiency of MOF immobilized BSA were discussed. The outcomes indicated that the binding between MOF-919 and BSA was due to the synergistic interplay of pore diffusion and surface adsorption mechanisms. Meanwhile, after the immobilization, the composite material (MOF-919@BSA) was developed as a new kind of chiral splitter that combined with polyethersulfone to form the MMM. As well as the concentration of feed solution, thickness of membrane, proportion of biocomposite materials in membrane, the penetration time, cycle index and the micro environment of BSA on the separation of chiral enantiomers from the MMMs were investigated. The chiral membrane had excellent selectivity and high flux in the process of transporting chiral enantiomers. After that, the reliability of the mechanism for chiral separation was demonstrated through molecular docking simulations. At the same time, MOF@BSA-PES mixed matrix membrane manifested superior performance compared with the majority of state-of-the-art chiral membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124057"},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143815367","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.memsci.2025.124063
Mehran Aliaskari , Harald Horn , Florencia Saravia
In this study, scaling in bipolar membrane electrodialysis (BPMED) was investigated in real time using a custom-made flow cell and Optical Coherence Tomography (OCT). Unlike previous studies that applied OCT in pressure- or thermal-driven membrane processes, this work demonstrates its use in electrodialysis for the first time, enabling in-situ observation and quantification of scaling on the basic side of the bipolar membrane under various operational conditions. The results revealed that higher flow rates and lower applied currents reduced scaling coverage and thickness, attributed to improved hydrodynamics and a lower pH shift. Increasing the system's buffer capacity through higher dissolved inorganic carbon (DIC) concentrations resulted in less scaling, whereas total removal of DIC drastically increased scaling formation due to the loss of buffering capacity, leading to extreme pH shifts. Furthermore, Mg(OH)2 was identified as the dominant scalant under high-pH conditions, confirming its major role in scaling formation in BPMED. Scaling formation was highly non-uniform, emphasizing the strong influence of hydrodynamic conditions and spacer geometry. These findings can be used in the future to develop and test improved fouling mitigation and cleaning strategies, enhancing BPMED performance and its application in CO2 capture and related processes.
{"title":"Real time monitoring of scaling behavior in bipolar membrane electrodialysis","authors":"Mehran Aliaskari , Harald Horn , Florencia Saravia","doi":"10.1016/j.memsci.2025.124063","DOIUrl":"10.1016/j.memsci.2025.124063","url":null,"abstract":"<div><div>In this study, scaling in bipolar membrane electrodialysis (BPMED) was investigated in real time using a custom-made flow cell and Optical Coherence Tomography (OCT). Unlike previous studies that applied OCT in pressure- or thermal-driven membrane processes, this work demonstrates its use in electrodialysis for the first time, enabling in-situ observation and quantification of scaling on the basic side of the bipolar membrane under various operational conditions. The results revealed that higher flow rates and lower applied currents reduced scaling coverage and thickness, attributed to improved hydrodynamics and a lower pH shift. Increasing the system's buffer capacity through higher dissolved inorganic carbon (DIC) concentrations resulted in less scaling, whereas total removal of DIC drastically increased scaling formation due to the loss of buffering capacity, leading to extreme pH shifts. Furthermore, Mg(OH)<sub>2</sub> was identified as the dominant scalant under high-pH conditions, confirming its major role in scaling formation in BPMED. Scaling formation was highly non-uniform, emphasizing the strong influence of hydrodynamic conditions and spacer geometry. These findings can be used in the future to develop and test improved fouling mitigation and cleaning strategies, enhancing BPMED performance and its application in CO<sub>2</sub> capture and related processes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"727 ","pages":"Article 124063"},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.memsci.2025.124066
Zhongming Xu , Nanjie Chen , Sheng Huang , Shuanjin Wang , Dongmei Han , Min Xiao , Yuezhong Meng
High temperature proton exchange membrane fuel cells (HT-PEMFCs) has become one of the most promising sustainable energy conversion technologies due to its cleanliness, high resistance to CO toxicity and simplified hydrothermal management. A major challenge is how to improve the acid retention in phosphoric acid (PA)-doped polymer electrolytes in HT-PEMFCs to obtain cells with extended durability. In this work, asymmetric PA-doped polybenzimidazole membranes (PA-APBI-ZrP(X)) with PA-doped poly [2,2‘-(p-oxydiphenyl)-5,5’-biphenylimidazole] (OPBI) membranes as the substrate and the OPBI/zirconium phosphate nanosheets composite coating layer (OPBI/ZrP(X)) on the cathode-contact side were prepared for the first time via hot pressure transfer method. The parallel distribution and high barrier property of the ZrP nanosheets constructed tortuous ion transport channels and mitigated the PA loss from membrane to the catalyst layer, which significantly improved the durability of HT-PEMFCs. The prepared PA-APBI-ZrP(20) membranes exhibited a low voltage decay rate in the 72 h accelerated stress test (AST), and the cell voltage achieved almost no decay (4.76 μV h−1) for 420 h at the operating current. The idea of cathode-side coating with a nanocomposite layer provides a feasible strategy to achieve the long-term operation of HT-PEMFCs.
{"title":"Zirconium phosphate nanosheets coated asymmetric polybenzimidazole membrane boosting the durability of HT-PEM fuel cells","authors":"Zhongming Xu , Nanjie Chen , Sheng Huang , Shuanjin Wang , Dongmei Han , Min Xiao , Yuezhong Meng","doi":"10.1016/j.memsci.2025.124066","DOIUrl":"10.1016/j.memsci.2025.124066","url":null,"abstract":"<div><div>High temperature proton exchange membrane fuel cells (HT-PEMFCs) has become one of the most promising sustainable energy conversion technologies due to its cleanliness, high resistance to CO toxicity and simplified hydrothermal management. A major challenge is how to improve the acid retention in phosphoric acid (PA)-doped polymer electrolytes in HT-PEMFCs to obtain cells with extended durability. In this work, asymmetric PA-doped polybenzimidazole membranes (PA-APBI-ZrP(X)) with PA-doped poly [2,2‘-(<em>p</em>-oxydiphenyl)-5,5’-biphenylimidazole] (OPBI) membranes as the substrate and the OPBI/zirconium phosphate nanosheets composite coating layer (OPBI/ZrP(X)) on the cathode-contact side were prepared for the first time via hot pressure transfer method. The parallel distribution and high barrier property of the ZrP nanosheets constructed tortuous ion transport channels and mitigated the PA loss from membrane to the catalyst layer, which significantly improved the durability of HT-PEMFCs. The prepared PA-APBI-ZrP(20) membranes exhibited a low voltage decay rate in the 72 h accelerated stress test (AST), and the cell voltage achieved almost no decay (4.76 μV h<sup>−1</sup>) for 420 h at the operating current. The idea of cathode-side coating with a nanocomposite layer provides a feasible strategy to achieve the long-term operation of HT-PEMFCs.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124066"},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.memsci.2025.124067
Qingnan Wang , Yanting Tang , Longjie Liu , Chenlu Liu , Keming Zhang , Xiaohe Tian , Xiaoting Feng , Rui Zhang , Yueyangchao Yu , Tianhe Gu , Bin Liu , Shaofei Wang
The scalable fabrication of large-area, defect-free metal-organic framework (MOF) membranes for precise gas separation is hindered by their intrinsic brittleness and polycrystalline defects. Herein, we present a molecular weaving strategy to construct an interwoven mixed matrix membrane of rigid 3D UiO-66 gel and flexible polyethyleneimine (PEI) polymers, achieving both structural robustness and tunable porosity. Glutaraldehyde crosslinking further stabilizes the hybrid framework, enhancing mechanical durability while refining pore dimensions to 0.35 nm, ideal for H2/CO2 sieving. The resultant ultrathin (∼50 nm) but flexible membranes, with UiO-66 content up to 46 wt%, exhibit superior separation performance, achieving a H2 permeance of 845 GPU and H2/CO2 selectivity of 16.8, surpassing the 2008 Robeson upper bound. Additionally, we demonstrated the fabrication of defect-free membranes ∼160 cm2, showcasing the scalable potential of this method. This work introduces a promising strategy for designing flexible, high-performance MOF-based separation systems, addressing urgent challenges in energy-efficient gas purification and carbon capture.
{"title":"Interwoven MOF gel – polymer network mixed matrix membranes for enhanced H2/CO2 separation","authors":"Qingnan Wang , Yanting Tang , Longjie Liu , Chenlu Liu , Keming Zhang , Xiaohe Tian , Xiaoting Feng , Rui Zhang , Yueyangchao Yu , Tianhe Gu , Bin Liu , Shaofei Wang","doi":"10.1016/j.memsci.2025.124067","DOIUrl":"10.1016/j.memsci.2025.124067","url":null,"abstract":"<div><div>The scalable fabrication of large-area, defect-free metal-organic framework (MOF) membranes for precise gas separation is hindered by their intrinsic brittleness and polycrystalline defects. Herein, we present a molecular weaving strategy to construct an interwoven mixed matrix membrane of rigid 3D UiO-66 gel and flexible polyethyleneimine (PEI) polymers, achieving both structural robustness and tunable porosity. Glutaraldehyde crosslinking further stabilizes the hybrid framework, enhancing mechanical durability while refining pore dimensions to 0.35 nm, ideal for H<sub>2</sub>/CO<sub>2</sub> sieving. The resultant ultrathin (∼50 nm) but flexible membranes, with UiO-66 content up to 46 wt%, exhibit superior separation performance, achieving a H<sub>2</sub> permeance of 845 GPU and H<sub>2</sub>/CO<sub>2</sub> selectivity of 16.8, surpassing the 2008 Robeson upper bound. Additionally, we demonstrated the fabrication of defect-free membranes ∼160 cm<sup>2</sup>, showcasing the scalable potential of this method. This work introduces a promising strategy for designing flexible, high-performance MOF-based separation systems, addressing urgent challenges in energy-efficient gas purification and carbon capture.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124067"},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-02DOI: 10.1016/j.memsci.2025.124064
Yurong Yin , Can Li , Daniel Yee Fan Ng , Rong Wang
Efficient Mg2+/Li+ separation is vital for lithium recovery from salt-lake, necessitating the advancement of nanofiltration membrane technologies. Current nanofiltration membranes have been enhanced through advanced materials and surface modification to enhance the targeted separation of Mg2+ and Li+. However, significant challenges still exist, including maintaining an optimal balance between high selectivity and permeability and ensuring cost-effectiveness for large-scale industrial adoption. Herein, we developed a novel nanofiltration membrane by integrating 3-bromopropyl trimethylammonium bromide (BPTAB) into the aqueous phase as an additive during interfacial polymerization. The modified membrane’s physicochemical properties and performances were evaluated against a control membrane prepared using tris(2-aminoethyl)amine and trimesoyl chloride on a polyethersulfone substrate. With BPTAB added, the positive charge densities on both top and bottom surfaces of the membrane selective layer were enhanced. Besides, the introduction of the BPTAB led to a reduced membrane pore size and a more uniform pore size distribution. Both the increased positive charge density and refined pore structure collectively contributed to the improved MgCl2 rejection and enhanced Mg2+/Li+ separation. The BPTAB-modified membrane exhibited a high pure water permeability of 23.5 L m−2 h−1 bar−1 and achieved a Mg2+/Li+ selectivity (SLi/Mg) of 24.8 in a 2000 ppm mixed solution with a Mg2+/Li+ ratio of 20, significantly surpassing the control membrane (SLi/Mg = 5.2). The results emphasize the considerable ability of BPTAB-modified membrane for efficient Mg2+/Li+ separation in lithium extraction applications.
{"title":"Quaternary ammonium-regulated fabrication of hollow fiber nanofiltration membrane for enhanced Mg2+/Li+ separation","authors":"Yurong Yin , Can Li , Daniel Yee Fan Ng , Rong Wang","doi":"10.1016/j.memsci.2025.124064","DOIUrl":"10.1016/j.memsci.2025.124064","url":null,"abstract":"<div><div>Efficient Mg<sup>2+</sup>/Li<sup>+</sup> separation is vital for lithium recovery from salt-lake, necessitating the advancement of nanofiltration membrane technologies. Current nanofiltration membranes have been enhanced through advanced materials and surface modification to enhance the targeted separation of Mg<sup>2+</sup> and Li<sup>+</sup>. However, significant challenges still exist, including maintaining an optimal balance between high selectivity and permeability and ensuring cost-effectiveness for large-scale industrial adoption. Herein, we developed a novel nanofiltration membrane by integrating 3-bromopropyl trimethylammonium bromide (BPTAB) into the aqueous phase as an additive during interfacial polymerization. The modified membrane’s physicochemical properties and performances were evaluated against a control membrane prepared using tris(2-aminoethyl)amine and trimesoyl chloride on a polyethersulfone substrate. With BPTAB added, the positive charge densities on both top and bottom surfaces of the membrane selective layer were enhanced. Besides, the introduction of the BPTAB led to a reduced membrane pore size and a more uniform pore size distribution. Both the increased positive charge density and refined pore structure collectively contributed to the improved MgCl<sub>2</sub> rejection and enhanced Mg<sup>2+</sup>/Li<sup>+</sup> separation. The BPTAB-modified membrane exhibited a high pure water permeability of 23.5 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> and achieved a Mg<sup>2+</sup>/Li<sup>+</sup> selectivity (S<sub>Li/Mg</sub>) of 24.8 in a 2000 ppm mixed solution with a Mg<sup>2+</sup>/Li<sup>+</sup> ratio of 20, significantly surpassing the control membrane (S<sub>Li/Mg</sub> = 5.2). The results emphasize the considerable ability of BPTAB-modified membrane for efficient Mg<sup>2+</sup>/Li<sup>+</sup> separation in lithium extraction applications.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124064"},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High-temperature nanofiltration (NF) technology is essential in various industrial applications. However, the thermal instability of thin-film composite (TFC) membranes remains inadequately addressed. As a crucial constituent of TFC NF membranes, substrate membrane is highly important to the thermal stability of TFC membranes. Herein, four commercial ultrafiltration membranes were used as substrates to fabricate TFC NF membranes via support-free interfacial polymerization, which generates polyamide selective layers with high crosslinking degree. Combining experimental characterizations and COMSOL Multiphysics® thermal-stress simulations, we decoupled the decisive roles of substrate glass transition temperature (Tg) and coefficient of thermal expansion (CTE) in determining membrane integrity at high temperature. Results show that TFC membranes supported by substrates with low Tg or high CTE exhibit a significant decline in MgSO4 rejection at high temperature. In contrast, substrates with high Tg and suitable CTE induce TFC membranes with a superior water permeance (33.4 L m-2 h-1 bar-1), a desirable MgSO4 rejection (96.4%), and good operation stability at 85 °C. This work reveals the roles of substrate membranes and demonstrates the design of thermally stable TFC NF membranes for high temperature separation.
{"title":"Effects of substrates on the thermal stability of thin-film composite polyamide nanofiltration membranes","authors":"Xiao-Wei Luo, Wan-Long Li, Wan-Ting Lin, Ping Fu, Zi-Lu Zhang, Hong-Yu Fan, Si-Yuan Zhang, Zi-Jun Zhang, Zhi-Kang Xu, Ling-Shu Wan","doi":"10.1016/j.memsci.2025.124062","DOIUrl":"10.1016/j.memsci.2025.124062","url":null,"abstract":"<div><div>High-temperature nanofiltration (NF) technology is essential in various industrial applications. However, the thermal instability of thin-film composite (TFC) membranes remains inadequately addressed. As a crucial constituent of TFC NF membranes, substrate membrane is highly important to the thermal stability of TFC membranes. Herein, four commercial ultrafiltration membranes were used as substrates to fabricate TFC NF membranes via support-free interfacial polymerization, which generates polyamide selective layers with high crosslinking degree. Combining experimental characterizations and COMSOL Multiphysics® thermal-stress simulations, we decoupled the decisive roles of substrate glass transition temperature (T<sub>g</sub>) and coefficient of thermal expansion (CTE) in determining membrane integrity at high temperature. Results show that TFC membranes supported by substrates with low T<sub>g</sub> or high CTE exhibit a significant decline in MgSO<sub>4</sub> rejection at high temperature. In contrast, substrates with high T<sub>g</sub> and suitable CTE induce TFC membranes with a superior water permeance (33.4 L m<sup>-2</sup> h<sup>-1</sup> bar<sup>-1</sup>), a desirable MgSO<sub>4</sub> rejection (96.4%), and good operation stability at 85 °C. This work reveals the roles of substrate membranes and demonstrates the design of thermally stable TFC NF membranes for high temperature separation.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124062"},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-02DOI: 10.1016/j.memsci.2025.124061
Fan Yang , Qiangqiang Yang , Jing Guo , Xiaoyu Tan , Junhui Huang , Yanqiu Zhang , Lu Shao
Self-standing COF membranes with precisely defined channels enable selective separation and rapid solvent transport, showing the potential to overcome the trade-off between selectivity and permeability. However, self-standing COF membranes formed through conventional interfacial polymerization often suffer from structural heterogeneity, resulting in numerous gaps and defects that impair membrane integrity and separation performance. In this work, we present a simple method to increase the structural homogeneity of COF membranes via a carbon quantum dot (CQD)-mediated interfacial polymerization process. CQDs controllably release amine monomers at the reaction interface, enabling the COF layer to nucleate and grow slowly, resulting in a highly ordered and uniform membrane structure. The resulting COF‒membrane composite membranes, characterized by uniform, dense, and smooth surfaces, achieve precise separation between dyes and salts and exhibit an exceptionally high water flux of 92.1 L/m2 h bar. Furthermore, the separation process of the COF membrane aligns with a pore flow model, where the permeation flux for different solvents inversely correlates with their viscosity, reaching up to 213.6 L/m2·h·bar for acetonitrile. This work offers a promising strategy for the fabrication of highly crystalline and structurally precise COF membranes for energy-efficient environmental remediation and resource recovery.
{"title":"CQD-mediated homogeneous covalent organic framework membranes for ultrafast molecular sieving","authors":"Fan Yang , Qiangqiang Yang , Jing Guo , Xiaoyu Tan , Junhui Huang , Yanqiu Zhang , Lu Shao","doi":"10.1016/j.memsci.2025.124061","DOIUrl":"10.1016/j.memsci.2025.124061","url":null,"abstract":"<div><div>Self-standing COF membranes with precisely defined channels enable selective separation and rapid solvent transport, showing the potential to overcome the trade-off between selectivity and permeability. However, self-standing COF membranes formed through conventional interfacial polymerization often suffer from structural heterogeneity, resulting in numerous gaps and defects that impair membrane integrity and separation performance. In this work, we present a simple method to increase the structural homogeneity of COF membranes via a carbon quantum dot (CQD)-mediated interfacial polymerization process. CQDs controllably release amine monomers at the reaction interface, enabling the COF layer to nucleate and grow slowly, resulting in a highly ordered and uniform membrane structure. The resulting COF‒membrane composite membranes, characterized by uniform, dense, and smooth surfaces, achieve precise separation between dyes and salts and exhibit an exceptionally high water flux of 92.1 L/m<sup>2</sup> h bar. Furthermore, the separation process of the COF membrane aligns with a pore flow model, where the permeation flux for different solvents inversely correlates with their viscosity, reaching up to 213.6 L/m<sup>2</sup>·h·bar for acetonitrile. This work offers a promising strategy for the fabrication of highly crystalline and structurally precise COF membranes for energy-efficient environmental remediation and resource recovery.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124061"},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143768322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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