Pub Date : 2025-12-16DOI: 10.1016/j.memsci.2025.125069
Yanmei Li , Xitai Cai , Chunjie Chen, Libo Li, Yali Zhao, Wufeng Wu, Yanying Wei
Metal-organic framework (MOF) nanosheet membranes are promising for H2 purification because their highly tunable pore networks permit precise control of the sieving aperture. However, unavoidable linker rotation in MOFs impedes precise molecular sieving, with the impact further amplified in low-dimensional 2D nanosheets due to increased conformational freedom. Herein, we establish a rational rigidity-control strategy in heterobimetallic Zn(100-x)Cox(Bim)(OAc) nanosheets achieved by in-situ dual-metal integration. Moderate Co2+ incorporation reinforces the framework rigidity while preserving structural integrity, which sharpens molecular sieving. At an optimal Co2+ content of ∼30 %, the Zn(100-x)Cox(Bim)(OAc) nanosheet membrane exhibits an exceptional H2/CO2 selectivity of 243, a 180 % improvement over the more flexible Zn(Bim)(OAc) membrane. However, excessive Co2+ incorporation induces structural disorder, demonstrating that an optimal balance between rigidity enhancement and structural integrity is crucial for maximizing separation performance, providing an opening avenue for rational design in 2D MOF nanosheet membranes.
{"title":"Rational rigidity control in heterobimetallic MOF nanosheets for precise molecular sieving","authors":"Yanmei Li , Xitai Cai , Chunjie Chen, Libo Li, Yali Zhao, Wufeng Wu, Yanying Wei","doi":"10.1016/j.memsci.2025.125069","DOIUrl":"10.1016/j.memsci.2025.125069","url":null,"abstract":"<div><div>Metal-organic framework (MOF) nanosheet membranes are promising for H<sub>2</sub> purification because their highly tunable pore networks permit precise control of the sieving aperture. However, unavoidable linker rotation in MOFs impedes precise molecular sieving, with the impact further amplified in low-dimensional 2D nanosheets due to increased conformational freedom. Herein, we establish a rational rigidity-control strategy in heterobimetallic Zn<sub>(100-x)</sub>Co<sub>x</sub>(Bim)(OAc) nanosheets achieved by in-situ dual-metal integration. Moderate Co<sup>2+</sup> incorporation reinforces the framework rigidity while preserving structural integrity, which sharpens molecular sieving. At an optimal Co<sup>2+</sup> content of ∼30 %, the Zn<sub>(100-x)</sub>Co<sub>x</sub>(Bim)(OAc) nanosheet membrane exhibits an exceptional H<sub>2</sub>/CO<sub>2</sub> selectivity of 243, a 180 % improvement over the more flexible Zn(Bim)(OAc) membrane. However, excessive Co<sup>2+</sup> incorporation induces structural disorder, demonstrating that an optimal balance between rigidity enhancement and structural integrity is crucial for maximizing separation performance, providing an opening avenue for rational design in 2D MOF nanosheet membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125069"},"PeriodicalIF":9.0,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787076","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 : 2025-12-15DOI: 10.1016/j.memsci.2025.125061
Dong Wang , Leyuan Zhou , Jian Zhang , Lihui Chen , Yubin Hong , Yaling Lin , Liulian Huang
In this study, the pore structure of cellulose-based nanofiltration (NF) membrane was modulated through solid phase keratinization of cellulose for efficient separation of dyes and salt ions. Increasing dryness of cellulose-based membrane resulted in shrinking pore structure and smoothing membrane surface, in which the hydrogen bonding interactions between cellulose molecules would be enhanced due to the escape of free water. As a result, the loose cellulose-based NF membrane with tailored pore structure could be used to finely separate small active organic molecules. The membrane with 75 % dryness exhibited satisfactory rejection of anionic dyes with a molecular weight higher than 400 Da (Congo red:98.81 %), while the membrane with 95 % dryness was able to reject anionic dyes with a molecular weight lower than 400 Da (Methyl orange:81.17 %) and cationic dyes (Bengal rose red = 98.36 %, Methylene blue:85.77 %). In addition, the M-75 % membrane exhibited a strong ability in salt/dye separation (Congo red:98.81 %, Na2SO4:5.31 %, NaCl:3.58 %) and possessed comparable pure water flux (175.88 L m−2 h−1), excellent anti-fouling properties (flux recovery rate >96 %), and long-term stability (decline rates <5 % in 24 h). This study provided a simple method to prepare the loose cellulose-based NF membrane with efficient separation of dye/salt.
{"title":"Modulating pore structure of cellulose-based nanofiltration membrane through solid phase keratinization of cellulose for highly efficient dye/salt separation","authors":"Dong Wang , Leyuan Zhou , Jian Zhang , Lihui Chen , Yubin Hong , Yaling Lin , Liulian Huang","doi":"10.1016/j.memsci.2025.125061","DOIUrl":"10.1016/j.memsci.2025.125061","url":null,"abstract":"<div><div>In this study, the pore structure of cellulose-based nanofiltration (NF) membrane was modulated through solid phase keratinization of cellulose for efficient separation of dyes and salt ions. Increasing dryness of cellulose-based membrane resulted in shrinking pore structure and smoothing membrane surface, in which the hydrogen bonding interactions between cellulose molecules would be enhanced due to the escape of free water. As a result, the loose cellulose-based NF membrane with tailored pore structure could be used to finely separate small active organic molecules. The membrane with 75 % dryness exhibited satisfactory rejection of anionic dyes with a molecular weight higher than 400 Da (Congo red:98.81 %), while the membrane with 95 % dryness was able to reject anionic dyes with a molecular weight lower than 400 Da (Methyl orange:81.17 %) and cationic dyes (Bengal rose red = 98.36 %, Methylene blue:85.77 %). In addition, the M-75 % membrane exhibited a strong ability in salt/dye separation (Congo red:98.81 %, Na<sub>2</sub>SO<sub>4</sub>:5.31 %, NaCl:3.58 %) and possessed comparable pure water flux (175.88 L m<sup>−2</sup> h<sup>−1</sup>), excellent anti-fouling properties (flux recovery rate >96 %), and long-term stability (decline rates <5 % in 24 h). This study provided a simple method to prepare the loose cellulose-based NF membrane with efficient separation of dye/salt.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125061"},"PeriodicalIF":9.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837107","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}
Traditional nanofiltration membranes fabricated via water/oil interface polymerization face two challenges, reduced water permeance caused by excessive polymerization rates, and the potential hazards associated with the use and storage of organic reagents (e.g., n-Hexane). Effective strategies are urgently needed to regulate the reaction process and ensure the safe and green preparation process. To address these issues, we proposed a green water/deep eutectic solvent (DES) interface polymerization (IP) strategy to prepare high-performance polyamide nanofiltration membranes. DES, prepared by mixing L-menthol and ethylene glycol, served as the solvent for acyl chloride monomers (trimethoyl chloride, TMC). DES possesses higher viscosity (54 mPa·s) to inhibit the diffusion of TMC, while the high interfacial tension of the DES/water system slowed the cross-phase transport of amine monomers (polyvinylamine, PVAm). This synergistic regulation of the overall interfacial polymerization process resulted in a thin (40 nm) and loose polyamide layer, much thinner than the polyamide layer prepared in n-Hexane/water system (98 nm). The prepared DES@IP membrane exhibited an ultrahigh water permeance of 61.5 L m−2 h−1 bar−1, while maintaining an exceptionally high dye/salt separation efficiency (separation factor of 230). This approach offers a novel solution for green and organic-free reagent-based interfacial polymerization and provides valuable insights into the potential application of high-performance polyamide nanofiltration membranes in dye desalination.
传统的通过水/油界面聚合制备的纳滤膜面临两个挑战：过高的聚合速率导致的水渗透性降低，以及与使用和储存有机试剂（如正己烷）相关的潜在危害。迫切需要有效的策略来规范反应过程，确保制备过程的安全和绿色。为了解决这些问题，我们提出了一种绿色水/深度共晶溶剂（DES）界面聚合（IP）策略来制备高性能聚酰胺纳滤膜。将l -薄荷醇和乙二醇混合制备DES，作为酰基氯单体（三甲酰氯，TMC）的溶剂。DES具有较高的粘度（54 mPa·s）来抑制TMC的扩散，而DES/水体系的高界面张力减缓了胺类单体（聚乙烯胺，PVAm）的跨相传输。这种对整个界面聚合过程的协同调节导致聚酰胺层薄（40 nm）且松散，比正己烷/水体系制备的聚酰胺层（98 nm）薄得多。制备的DES@IP膜具有61.5 L m−2 h−1 bar−1的超高透水性，同时保持了极高的染料/盐分离效率（分离系数为230）。这种方法为绿色和无有机试剂的界面聚合提供了一种新的解决方案，并为高性能聚酰胺纳滤膜在染料脱盐中的潜在应用提供了有价值的见解。
{"title":"Green preparation of nanofiltration membranes with high permeability and selectivity via deep eutectic solvent-mediated interfacial polymerization for efficient dye desalination","authors":"Jian Dong, Jianwei Li, Liangliang Dong, Tatsuo Kaneko, Weifu Dong, Dongjian Shi, Mingqing Chen","doi":"10.1016/j.memsci.2025.125062","DOIUrl":"10.1016/j.memsci.2025.125062","url":null,"abstract":"<div><div>Traditional nanofiltration membranes fabricated via water/oil interface polymerization face two challenges, reduced water permeance caused by excessive polymerization rates, and the potential hazards associated with the use and storage of organic reagents (e.g., n-Hexane). Effective strategies are urgently needed to regulate the reaction process and ensure the safe and green preparation process. To address these issues, we proposed a green water/deep eutectic solvent (DES) interface polymerization (IP) strategy to prepare high-performance polyamide nanofiltration membranes. DES, prepared by mixing L-menthol and ethylene glycol, served as the solvent for acyl chloride monomers (trimethoyl chloride, TMC). DES possesses higher viscosity (54 mPa·s) to inhibit the diffusion of TMC, while the high interfacial tension of the DES/water system slowed the cross-phase transport of amine monomers (polyvinylamine, PVAm). This synergistic regulation of the overall interfacial polymerization process resulted in a thin (40 nm) and loose polyamide layer, much thinner than the polyamide layer prepared in n-Hexane/water system (98 nm). The prepared DES@IP membrane exhibited an ultrahigh water permeance of 61.5 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>, while maintaining an exceptionally high dye/salt separation efficiency (separation factor of 230). This approach offers a novel solution for green and organic-free reagent-based interfacial polymerization and provides valuable insights into the potential application of high-performance polyamide nanofiltration membranes in dye desalination.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125062"},"PeriodicalIF":9.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787095","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 : 2025-12-15DOI: 10.1016/j.memsci.2025.125060
Liuyan Shen , Qian Liang , Wenhui Song , Han Zhu , Qiang Ma , Wei Fang , Zhenxin Zhang , Hua Jin , Jungkyu Choi , Yanshuo Li
Despite energy-efficient separations, feasible defect control and scale-up in metal-organic framework membrane manufacturing largely remain limited. In this study, we experimentally and theoretically elucidated the liquid-phase crystallization of zeolitic imidazolate framework-8 (ZIF-8), whose evolution depends on solvent polarity, metal precursor, and ion solvation. Such insights into direct in situ growth allowed for rigorous time-resolved analysis on ZIF-8 membrane formation. In particular, electrostatically assisted heterogeneous nucleation on hydroxylated α-Al2O3 has been verified under mildly alkaline conditions. Guided by these findings, coordinated tuning of composition and temperature in optimal solvent (here, water) yielded defect-minimized ZIF-8 membranes on α-Al2O3 disc supports, showing excellent C3H6/C3H8 separation performance (its separation factor up to 128) and remarkable pressure resistance and thermal stability. Furthermore, the in situ strategy was successfully extended to α-Al2O3 tube supports: The resulting tubular membranes showed C3H6/C3H8 separation factors of 79.3 ± 5.4. Desirably, a four-channel membrane module, now having an effective area of 150 cm2, exhibited good long-term C3H6/C3H8 separation stability. Finally, the in situ method was effective in synthesizing large-area ZIF-8 membranes on flat polyacrylonitrile (PAN) supports (300 cm2), with satisfactory mechanical strength and C3H6/C3H8 separation performance comparable to those of the α-Al2O3 disc- or tube-supported ones. In this work, we proposed a fundamental solution (rather than a trial-and-error approach) for in situ ZIF-8 membrane growth independent of supports: Mechanism-driven control with manufacturable processing provided universal and practical design rules for high-performance ZIF-8 membranes.
{"title":"In situ growth of defect-minimized ZIF-8 membranes suitable for practical propylene/propane separation processes: Elucidation of mechanistic insights into ZIF-8 crystal growth led to an optimal synthetic route","authors":"Liuyan Shen , Qian Liang , Wenhui Song , Han Zhu , Qiang Ma , Wei Fang , Zhenxin Zhang , Hua Jin , Jungkyu Choi , Yanshuo Li","doi":"10.1016/j.memsci.2025.125060","DOIUrl":"10.1016/j.memsci.2025.125060","url":null,"abstract":"<div><div>Despite energy-efficient separations, feasible defect control and scale-up in metal-organic framework membrane manufacturing largely remain limited. In this study, we experimentally and theoretically elucidated the liquid-phase crystallization of zeolitic imidazolate framework-8 (ZIF-8), whose evolution depends on solvent polarity, metal precursor, and ion solvation. Such insights into direct <em>in situ</em> growth allowed for rigorous time-resolved analysis on ZIF-8 membrane formation. In particular, electrostatically assisted heterogeneous nucleation on hydroxylated α-Al<sub>2</sub>O<sub>3</sub> has been verified under mildly alkaline conditions. Guided by these findings, coordinated tuning of composition and temperature in optimal solvent (here, water) yielded defect-minimized ZIF-8 membranes on α-Al<sub>2</sub>O<sub>3</sub> disc supports, showing excellent C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation performance (its separation factor up to 128) and remarkable pressure resistance and thermal stability. Furthermore, the <em>in situ</em> strategy was successfully extended to α-Al<sub>2</sub>O<sub>3</sub> tube supports: The resulting tubular membranes showed C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation factors of 79.3 ± 5.4. Desirably, a four-channel membrane module, now having an effective area of 150 cm<sup>2</sup>, exhibited good long-term C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation stability. Finally, the <em>in situ</em> method was effective in synthesizing large-area ZIF-8 membranes on flat polyacrylonitrile (PAN) supports (300 cm<sup>2</sup>), with satisfactory mechanical strength and C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation performance comparable to those of the α-Al<sub>2</sub>O<sub>3</sub> disc- or tube-supported ones. In this work, we proposed a fundamental solution (rather than a trial-and-error approach) for <em>in situ</em> ZIF-8 membrane growth independent of supports: Mechanism-driven control with manufacturable processing provided universal and practical design rules for high-performance ZIF-8 membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125060"},"PeriodicalIF":9.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837108","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 : 2025-12-15DOI: 10.1016/j.memsci.2025.125064
Jun Seok Hwang , So Youn Lee , Chae Young Go , Ki Chul Kim , Jong Hak Kim
Growing environmental restrictions on fluorinated materials underscore the need for sustainable reprocessing strategies that retain the superior performance of perfluorosulfonic acid (PFSA) membranes such as Nafion, while reducing the high energy demands of conventional fabrication. Traditional reprocessing via solution casting (SC) in high-boiling solvents requires prolonged thermal and vacuum drying (>24 h). Here, we present a rapid and energy-efficient gel-mediated densification (GMD) method for reprocessing dense Nafion membranes. The process involves brief heating of a dilute Nafion solution at 80 °C for 2 h to induce concentration, followed by immersion in a water nonsolvent, enabling rapid solvent extraction and direct membrane densification without pore formation. Ternary phase mapping, rheological analysis, in situ FTIR, and SEM collectively demonstrate that GMD promotes homogeneous densification rather than nonsolvent-induced phase separation. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations further reveal that gel formation arises from coupled thermodynamic and kinetic effects: strong Nafion-water interactions drive gel network formation, while restricted water diffusion kinetically stabilizes the gel phase. This synergistic mechanism yields uniform, defect-free membranes with ion-exchange capacity, water uptake, proton conductivity, mechanical strength and gas permeability comparable to those of SC-cast Nafion. Overall, the GMD strategy provides a simple, low-energy, and scalable route for sustainable Nafion membrane reprocessing without compromising performance.
{"title":"Rapid and energy-efficient reprocessing of Nafion membranes via gel-mediated densification","authors":"Jun Seok Hwang , So Youn Lee , Chae Young Go , Ki Chul Kim , Jong Hak Kim","doi":"10.1016/j.memsci.2025.125064","DOIUrl":"10.1016/j.memsci.2025.125064","url":null,"abstract":"<div><div>Growing environmental restrictions on fluorinated materials underscore the need for sustainable reprocessing strategies that retain the superior performance of perfluorosulfonic acid (PFSA) membranes such as Nafion, while reducing the high energy demands of conventional fabrication. Traditional reprocessing via solution casting (SC) in high-boiling solvents requires prolonged thermal and vacuum drying (>24 h). Here, we present a rapid and energy-efficient gel-mediated densification (GMD) method for reprocessing dense Nafion membranes. The process involves brief heating of a dilute Nafion solution at 80 °C for 2 h to induce concentration, followed by immersion in a water nonsolvent, enabling rapid solvent extraction and direct membrane densification without pore formation. Ternary phase mapping, rheological analysis, in situ FTIR, and SEM collectively demonstrate that GMD promotes homogeneous densification rather than nonsolvent-induced phase separation. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations further reveal that gel formation arises from coupled thermodynamic and kinetic effects: strong Nafion-water interactions drive gel network formation, while restricted water diffusion kinetically stabilizes the gel phase. This synergistic mechanism yields uniform, defect-free membranes with ion-exchange capacity, water uptake, proton conductivity, mechanical strength and gas permeability comparable to those of SC-cast Nafion. Overall, the GMD strategy provides a simple, low-energy, and scalable route for sustainable Nafion membrane reprocessing without compromising performance.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125064"},"PeriodicalIF":9.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837182","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 : 2025-12-14DOI: 10.1016/j.memsci.2025.125065
Fan Wang , Qiaobei Dong , Dinesh Kumar Behera , Weiwei Xu , Shiguang Li , Miao Yu
Nanoconfined ionic liquid (NCIL) membranes emerge as a highly promising candidate for gas separation due to the high-pressure durability, high gas selectivity, and ease of regeneration. However, the scalability and stability of liquid-based membranes for practical applications remain debatable. Herein, we demonstrated an industrially viable NCIL membrane for efficient CO2 capture from real coal-fired flue gas, via conducting a field testing using 1000 cm2 hollow fiber membrane modules at the National Carbon Capture Center (NCCC) in Wilsonville, AL, USA. Prior to the field testing, the gas separation performance was systematically evaluated using simulated flue gas to determine the optimal membrane structure and operation conditions. When using real flue gas in field testing, the membrane module demonstrated excellent and stable gas separation performance with stage cut for 8 days, with a log-mean CO2 permeance of 525 GPU and CO2/N2 selectivity of 488 at 70 °C. Apart from high CO2 capture rate up to 47 %, the membrane was capable of elevating the CO2 dry-basis purity from 10.4 % to 97 % in a single stage. The field-testing results represent the first successful module-level demonstration of NCIL membrane system and further validate its potential for industrial CO2 separation. Furthermore, this scale-up process is expected to serve as a platform or template for scaling up other task-specific liquid-based (TSIL) membranes, while largely mitigating the effects of substrate quality.
{"title":"Scale-up and field testing of nanoconfined ionic liquid membranes for CO2 capture from real flue gas","authors":"Fan Wang , Qiaobei Dong , Dinesh Kumar Behera , Weiwei Xu , Shiguang Li , Miao Yu","doi":"10.1016/j.memsci.2025.125065","DOIUrl":"10.1016/j.memsci.2025.125065","url":null,"abstract":"<div><div>Nanoconfined ionic liquid (NCIL) membranes emerge as a highly promising candidate for gas separation due to the high-pressure durability, high gas selectivity, and ease of regeneration. However, the scalability and stability of liquid-based membranes for practical applications remain debatable. Herein, we demonstrated an industrially viable NCIL membrane for efficient CO<sub>2</sub> capture from real coal-fired flue gas, via conducting a field testing using 1000 cm<sup>2</sup> hollow fiber membrane modules at the National Carbon Capture Center (NCCC) in Wilsonville, AL, USA. Prior to the field testing, the gas separation performance was systematically evaluated using simulated flue gas to determine the optimal membrane structure and operation conditions. When using real flue gas in field testing, the membrane module demonstrated excellent and stable gas separation performance with stage cut for 8 days, with a log-mean CO<sub>2</sub> permeance of 525 GPU and CO<sub>2</sub>/N<sub>2</sub> selectivity of 488 at 70 °C. Apart from high CO<sub>2</sub> capture rate up to 47 %, the membrane was capable of elevating the CO<sub>2</sub> dry-basis purity from 10.4 % to 97 % in a single stage. The field-testing results represent the first successful module-level demonstration of NCIL membrane system and further validate its potential for industrial CO<sub>2</sub> separation. Furthermore, this scale-up process is expected to serve as a platform or template for scaling up other task-specific liquid-based (TSIL) membranes, while largely mitigating the effects of substrate quality.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125065"},"PeriodicalIF":9.0,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837185","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 : 2025-12-14DOI: 10.1016/j.memsci.2025.125066
Jaeyu Lee , Haeyoung Lee , Shinyoung Lee , Woo-Jin Song , Kyung Jin Lee
Fiber-based nonwoven membrane has been considered as high-performance separator for Li-ion battery to overcome low ion conductivity, and to improve energy density of conventional separator. In this study, we fabricated polyacrylonitrile (PAN) nonwoven separators through syringeless electrospinning that can increase the production rate and density of nonwoven web. Furthermore, surface modification was carried out via vapor phase treatment (VPT), introducing ethylenediamine (EDA) and ethanolamine (EtA) which have different functional end groups. Porous morphologies of nonwoven web were maintained stably even in amine-modified PAN separators after VPT and roll pressing, and these amine modifications facilitated high electrolyte affinity and polarity, resulting in the outstanding ion conductivity (3.01 mS cm−1) and Li+ transference number (0.72), especially in the case of EtA-modified PAN separator (PAN@EtA). Moreover, LiNi0.6Co0.2Mn0.2O2 (NCM622)/graphite full cell with PAN@EtA separator exhibited discharge capacity of 124.09 mAh g−1 at 10 C then recovered 93 % at 0.5 C, and capacity retention of 79.9 % after 350 cycles at 0.5 C.
纤维基非织造膜克服了锂离子电池的低电导率，提高了常规隔膜的能量密度，成为锂离子电池的高性能隔膜。本研究采用无注射器静电纺丝法制备了聚丙烯腈（PAN）非织造膜，提高了非织造网的生产率和密度。此外，通过气相处理（VPT）对其进行表面改性，引入具有不同官能团的乙二胺（EDA）和乙醇胺（EtA）。经VPT和滚压处理后，胺改性的PAN隔膜仍能保持非织造网的孔隙形态，且具有较高的电解质亲和性和极性，离子电导率（3.01 mS cm−1）和Li+转移数（0.72）显著提高，尤其是eta改性的PAN隔膜（PAN@EtA）。此外，采用PAN@EtA分离器的LiNi0.6Co0.2Mn0.2O2 (NCM622)/石墨全电池在10℃下的放电容量为124.09 mAh g−1,0.5℃下的放电容量回收率为93%，0.5℃下循环350次后的容量保留率为79.9%。
{"title":"Electrospun nanofiber based LiB separator with tunable surface functional groups via vapor phase treatment","authors":"Jaeyu Lee , Haeyoung Lee , Shinyoung Lee , Woo-Jin Song , Kyung Jin Lee","doi":"10.1016/j.memsci.2025.125066","DOIUrl":"10.1016/j.memsci.2025.125066","url":null,"abstract":"<div><div>Fiber-based nonwoven membrane has been considered as high-performance separator for Li-ion battery to overcome low ion conductivity, and to improve energy density of conventional separator. In this study, we fabricated polyacrylonitrile (PAN) nonwoven separators through syringeless electrospinning that can increase the production rate and density of nonwoven web. Furthermore, surface modification was carried out via vapor phase treatment (VPT), introducing ethylenediamine (EDA) and ethanolamine (EtA) which have different functional end groups. Porous morphologies of nonwoven web were maintained stably even in amine-modified PAN separators after VPT and roll pressing, and these amine modifications facilitated high electrolyte affinity and polarity, resulting in the outstanding ion conductivity (3.01 mS cm<sup>−1</sup>) and Li<sup>+</sup> transference number (0.72), especially in the case of EtA-modified PAN separator (PAN@EtA). Moreover, LiNi<sub>0.6</sub>Co<sub>0.2</sub>Mn<sub>0.2</sub>O<sub>2</sub> (NCM622)/graphite full cell with PAN@EtA separator exhibited discharge capacity of 124.09 mAh g<sup>−1</sup> at 10 C then recovered 93 % at 0.5 C, and capacity retention of 79.9 % after 350 cycles at 0.5 C.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125066"},"PeriodicalIF":9.0,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787093","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 : 2025-12-13DOI: 10.1016/j.memsci.2025.125059
Jiadi Ying , Zhen Cui , Lei Tu , Tiancun Liu , Song Lu , Qi Shen , Min Guo , Yeqing Wang , Zhen Yang , Minfeng Zeng , Zhixin Yu , Xingzhong Cao , Yuqing Lin
The development of high-performance cation exchange membranes (CEMs) with precise ion selectivity is crucial for electrodialysis applications, such as lithium extraction from salt-lake brines. However, conventional membrane materials often face a trade-off between high ion permeability and selectivity. In this work, we engineered a novel ionic cross-linked microporous membrane by blending sulfonated poly(ether ether ketone) (SPEEK) with a quaternized polymer of intrinsic microporosity (QPIM). This strategy leverages acid-base pair interactions between the sulfonic acid groups of SPEEK and the quaternary ammonium groups of QPIM to create well-defined sub-nanometer-scale ion transport channels. The optimized QPIM/SPEEK membrane (QPIM15) exhibits an exceptional Li+/Mg2+ selectivity of 6.98 and a high Li + permeation flux of 1.9 mol m−2 h−1, outperforming the pristine SPEEK and commercial CSO membranes. Comprehensive characterization and molecular dynamics simulations demonstrate that the enhanced performance originates from the synergy between size-sieving effects of narrowed microporous channels and electrostatic repulsion of cationic quaternary ammonium groups. This work provides a facile and effective approach for designing advanced ion-selective membranes, demonstrating great potential for efficient lithium-ion separation and other electrodialysis processes.
{"title":"Polymers with intrinsic microporosity engineered via acid-base pairs for highly selective lithium-ion transport channels","authors":"Jiadi Ying , Zhen Cui , Lei Tu , Tiancun Liu , Song Lu , Qi Shen , Min Guo , Yeqing Wang , Zhen Yang , Minfeng Zeng , Zhixin Yu , Xingzhong Cao , Yuqing Lin","doi":"10.1016/j.memsci.2025.125059","DOIUrl":"10.1016/j.memsci.2025.125059","url":null,"abstract":"<div><div>The development of high-performance cation exchange membranes (CEMs) with precise ion selectivity is crucial for electrodialysis applications, such as lithium extraction from salt-lake brines. However, conventional membrane materials often face a trade-off between high ion permeability and selectivity. In this work, we engineered a novel ionic cross-linked microporous membrane by blending sulfonated poly(ether ether ketone) (SPEEK) with a quaternized polymer of intrinsic microporosity (QPIM). This strategy leverages acid-base pair interactions between the sulfonic acid groups of SPEEK and the quaternary ammonium groups of QPIM to create well-defined sub-nanometer-scale ion transport channels. The optimized QPIM/SPEEK membrane (QPIM15) exhibits an exceptional Li<sup>+</sup>/Mg<sup>2+</sup> selectivity of 6.98 and a high Li <sup>+</sup> permeation flux of 1.9 mol m<sup>−2</sup> h<sup>−1</sup>, outperforming the pristine SPEEK and commercial CSO membranes. Comprehensive characterization and molecular dynamics simulations demonstrate that the enhanced performance originates from the synergy between size-sieving effects of narrowed microporous channels and electrostatic repulsion of cationic quaternary ammonium groups. This work provides a facile and effective approach for designing advanced ion-selective membranes, demonstrating great potential for efficient lithium-ion separation and other electrodialysis processes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125059"},"PeriodicalIF":9.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787091","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 : 2025-12-13DOI: 10.1016/j.memsci.2025.125058
Huiyuan Chen , Qing Wang , Nong Xu , Qiao Liu , Fengshan Yu , Meng Guo , Bin Wang , Rongfei Zhou , Weihong Xing
Zeolite membranes used in pervaporation (PV) often present a trade-off between thickness and quality: thinner selective layers offer higher flux but are prone to nonselective defects. In this study, an ultradilute precursor solution combined with nanoseeds (15–25 nm) was employed for the first time to fabricate high-performance, ultrathin FAU zeolite membranes on tubular α-Al2O3 supports. The effects of synthesis parameters (precursor concentration, SiO2/Al2O3 ratio, crystallization temperature and time) on the membrane microstructure and PV performance were systematically investigated. The results show that the nanoseeds form a dense seed layer to effectively suppress defect formation, while the ultradilute precursor solution markedly reduces the rate of crystal growth, which thereby enables precise control over membrane thickness. Under optimized conditions (H2O/Al2O3 = 5,000, SiO2/Al2O3 = 9, 80 °C for 5 h), a pure-phase FAU membrane with an intergrown, defect-free microstructure was obtained at a thickness of approximately 1.61 μm. The membrane demonstrated excellent PV dehydration performance across representative water/organic solvent binary mixtures (ethanol, acetone, isopropanol, n-butanol, and dimethyl carbonate), which underscores its broad applicability. For example, the membrane achieved separation factors of 549 at 75 °C, 234 at 55 °C, and 1304 at 70 °C for binary mixtures containing 10 wt% water of ethanol, acetone, and isopropanol, respectively, with corresponding total fluxes of 2.29, 1.46, and 3.64 kg/(m2 h), respectively. In addition, the effect of operating parameters on PV performance was systematically examined and revealed that PV dehydration through the FAU membrane follows an adsorption-diffusion mechanism, with the hydrophilic FAU pores preferentially adsorbing water molecules to enable selective and rapid transport. In this study, high-quality ultrathin FAU membranes were successfully fabricated through the synergistic combination of an ultradilute precursor solution and nanoseeds. This strategy provides a promising route for the fabrication of zeolite membranes.
{"title":"Ultrathin FAU zeolite membranes via an ultradilute precursor-nanoseed strategy: synthesis optimization and pervaporation dehydration performance","authors":"Huiyuan Chen , Qing Wang , Nong Xu , Qiao Liu , Fengshan Yu , Meng Guo , Bin Wang , Rongfei Zhou , Weihong Xing","doi":"10.1016/j.memsci.2025.125058","DOIUrl":"10.1016/j.memsci.2025.125058","url":null,"abstract":"<div><div>Zeolite membranes used in pervaporation (PV) often present a trade-off between thickness and quality: thinner selective layers offer higher flux but are prone to nonselective defects. In this study, an ultradilute precursor solution combined with nanoseeds (15–25 nm) was employed for the first time to fabricate high-performance, ultrathin FAU zeolite membranes on tubular α-Al<sub>2</sub>O<sub>3</sub> supports. The effects of synthesis parameters (precursor concentration, SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratio, crystallization temperature and time) on the membrane microstructure and PV performance were systematically investigated. The results show that the nanoseeds form a dense seed layer to effectively suppress defect formation, while the ultradilute precursor solution markedly reduces the rate of crystal growth, which thereby enables precise control over membrane thickness. Under optimized conditions (H<sub>2</sub>O/Al<sub>2</sub>O<sub>3</sub> = 5,000, SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> = 9, 80 °C for 5 h), a pure-phase FAU membrane with an intergrown, defect-free microstructure was obtained at a thickness of approximately 1.61 μm. The membrane demonstrated excellent PV dehydration performance across representative water/organic solvent binary mixtures (ethanol, acetone, isopropanol, n-butanol, and dimethyl carbonate), which underscores its broad applicability. For example, the membrane achieved separation factors of 549 at 75 °C, 234 at 55 °C, and 1304 at 70 °C for binary mixtures containing 10 wt% water of ethanol, acetone, and isopropanol, respectively, with corresponding total fluxes of 2.29, 1.46, and 3.64 kg/(m<sup>2</sup> h), respectively. In addition, the effect of operating parameters on PV performance was systematically examined and revealed that PV dehydration through the FAU membrane follows an adsorption-diffusion mechanism, with the hydrophilic FAU pores preferentially adsorbing water molecules to enable selective and rapid transport. In this study, high-quality ultrathin FAU membranes were successfully fabricated through the synergistic combination of an ultradilute precursor solution and nanoseeds. This strategy provides a promising route for the fabrication of zeolite membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125058"},"PeriodicalIF":9.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787510","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 : 2025-12-12DOI: 10.1016/j.memsci.2025.125056
Qian Xu , Weijuan Guo , Ruonan Shi , Zhiling Yang , Xiaobin Wang , Feichao Wu
Developing advanced membrane materials, represented by MOF membranes, is crucial for the efficient separation of butane isomers, which are important petrochemical industrial raw materials. However, this area has received limited attention to date. In this work, MIL-140A series membranes were successfully prepared on α-Al2O3 ceramic substrates by metal precursor induction method, and were attempted for the separation of butane isomers. The developed MOF membranes exhibit impressive performance in separating n-butane/isobutane mixtures, which is attributed to their appropriate sieve apertures and preferential adsorption of n-butane. This mechanism can be described as size-based sieving assisted by preferential adsorption. Owing to its smaller sieve aperture, the performance of MIL-140A-NH2 membrane was superior to that of the MIL-140A membrane, showing a n-butane permeance of 136 GPU and an ideal selectivity of 25.4. The excellent separation performance was maintained under varying testing conditions, including operating temperature, operating pressure, feed composition, and testing duration. This work provides a useful reference for the development of membranes for industrial separation of butane isomers.
{"title":"Synthesis of robust MIL-140A series membranes for efficient butane isomer separation","authors":"Qian Xu , Weijuan Guo , Ruonan Shi , Zhiling Yang , Xiaobin Wang , Feichao Wu","doi":"10.1016/j.memsci.2025.125056","DOIUrl":"10.1016/j.memsci.2025.125056","url":null,"abstract":"<div><div>Developing advanced membrane materials, represented by MOF membranes, is crucial for the efficient separation of butane isomers, which are important petrochemical industrial raw materials. However, this area has received limited attention to date. In this work, MIL-140A series membranes were successfully prepared on α-Al<sub>2</sub>O<sub>3</sub> ceramic substrates by metal precursor induction method, and were attempted for the separation of butane isomers. The developed MOF membranes exhibit impressive performance in separating n-butane/isobutane mixtures, which is attributed to their appropriate sieve apertures and preferential adsorption of n-butane. This mechanism can be described as size-based sieving assisted by preferential adsorption. Owing to its smaller sieve aperture, the performance of MIL-140A-NH<sub>2</sub> membrane was superior to that of the MIL-140A membrane, showing a n-butane permeance of 136 GPU and an ideal selectivity of 25.4. The excellent separation performance was maintained under varying testing conditions, including operating temperature, operating pressure, feed composition, and testing duration. This work provides a useful reference for the development of membranes for industrial separation of butane isomers.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125056"},"PeriodicalIF":9.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787094","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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