Pub Date : 2025-12-12DOI: 10.1016/j.memsci.2025.125057
Kai Li , Yu-Ren Xue , Guang-Chang Xu , Hao-Cheng Yang , Zhi-Kang Xu
Supported ionic liquid membranes (SILMs) present exceptional selectivity in CO2 separation, but their practical application has been limited by extremely low permeance arising from high mass transfer resistance through the liquid phase. To overcome this limitation, we constructed an ultrathin ionic liquid (IL) selective layer by confining the liquid phase within a Janus substrate, referred to as Janus-confined ionic liquid membranes (JCILMs). The reduced IL thickness effectively lowers the transport resistance of CO2, thereby leading to a substantial enhancement in CO2 permeance. The Janus substrates were prepared via single-sided atomic layer deposition, where the thickness of the IL-philic layer could be adjusted by the deposition parameters such as the deposition cycle number and the precursor pulse time. The IL layer thickness is reduced from 180 μm to 30 μm. Corresponding JCILM performs a CO2 permeance of approximately 17 GPU with an ideal CO2/N2 selectivity of 70, representing a 19-fold permeance increase over the conventional SILM. The design of JCILMs broadens the application scope of Janus membranes and offers a novel strategy for the development of next-generation SILMs.
{"title":"Janus-confined ionic liquid membranes for boosted CO2 separation","authors":"Kai Li , Yu-Ren Xue , Guang-Chang Xu , Hao-Cheng Yang , Zhi-Kang Xu","doi":"10.1016/j.memsci.2025.125057","DOIUrl":"10.1016/j.memsci.2025.125057","url":null,"abstract":"<div><div>Supported ionic liquid membranes (SILMs) present exceptional selectivity in CO<sub>2</sub> separation, but their practical application has been limited by extremely low permeance arising from high mass transfer resistance through the liquid phase. To overcome this limitation, we constructed an ultrathin ionic liquid (IL) selective layer by confining the liquid phase within a Janus substrate, referred to as Janus-confined ionic liquid membranes (JCILMs). The reduced IL thickness effectively lowers the transport resistance of CO<sub>2</sub>, thereby leading to a substantial enhancement in CO<sub>2</sub> permeance. The Janus substrates were prepared via single-sided atomic layer deposition, where the thickness of the IL-philic layer could be adjusted by the deposition parameters such as the deposition cycle number and the precursor pulse time. The IL layer thickness is reduced from 180 μm to 30 μm. Corresponding JCILM performs a CO<sub>2</sub> permeance of approximately 17 GPU with an ideal CO<sub>2</sub>/N<sub>2</sub> selectivity of 70, representing a 19-fold permeance increase over the conventional SILM. The design of JCILMs broadens the application scope of Janus membranes and offers a novel strategy for the development of next-generation SILMs.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125057"},"PeriodicalIF":9.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787113","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 : 2025-12-11DOI: 10.1016/j.memsci.2025.125055
Hengxin Li , Kai Miao , Mei-ling Liu , Kecheng Guan , Dong Zou , Hideto Matsuyama
High-performance ceramic membranes are essential for membrane distillation (MD) treatment of high-salinity wastewater, yet achieving both high flux and strong rejection remains challenging. This study proposes a cross-layer construction strategy in which a polymer pre-filling approach is employed to fabricate a bi-layer silicon carbide (SiC) ceramic membrane without penetration, thereby significantly reducing mass-transfer resistance in vacuum membrane distillation (VMD). After optimization, the SiC support was sintered at 1350 °C, and a pre-filling concentration of 10 wt% PVB was identified as critical for preventing particle penetration and ensuring robust interfacial bonding. The membrane layer, prepared from a slurry with 15 wt% solid content and sintered at 1000 °C, exhibited a defect-free structure. Following fluorination, the membrane achieved a water contact angle of 139.6°. Computational fluid dynamics (CFD) simulations confirmed that the pre-filling strategy markedly reduces mass-transfer resistance compared with traditional intermediate-layer approaches. In VMD tests, the membrane delivered high fluxes of 34.89 and 28.40 kg·m-2·h-1 under feed salinities of 35 and 100 g·L-1 NaCl, respectively, while maintaining a salt rejection above 99.9 % and stable performance over 24 h. This work provides an effective pathway for designing high-flux ceramic membranes for MD.
{"title":"Cross-layer construction of ceramic membranes with minimizing transfer resistance for membrane distillation","authors":"Hengxin Li , Kai Miao , Mei-ling Liu , Kecheng Guan , Dong Zou , Hideto Matsuyama","doi":"10.1016/j.memsci.2025.125055","DOIUrl":"10.1016/j.memsci.2025.125055","url":null,"abstract":"<div><div>High-performance ceramic membranes are essential for membrane distillation (MD) treatment of high-salinity wastewater, yet achieving both high flux and strong rejection remains challenging. This study proposes a cross-layer construction strategy in which a polymer pre-filling approach is employed to fabricate a bi-layer silicon carbide (SiC) ceramic membrane without penetration, thereby significantly reducing mass-transfer resistance in vacuum membrane distillation (VMD). After optimization, the SiC support was sintered at 1350 °C, and a pre-filling concentration of 10 wt% PVB was identified as critical for preventing particle penetration and ensuring robust interfacial bonding. The membrane layer, prepared from a slurry with 15 wt% solid content and sintered at 1000 °C, exhibited a defect-free structure. Following fluorination, the membrane achieved a water contact angle of 139.6°. Computational fluid dynamics (CFD) simulations confirmed that the pre-filling strategy markedly reduces mass-transfer resistance compared with traditional intermediate-layer approaches. In VMD tests, the membrane delivered high fluxes of 34.89 and 28.40 kg·m<sup>-2</sup>·h<sup>-1</sup> under feed salinities of 35 and 100 g·L<sup>-1</sup> NaCl, respectively, while maintaining a salt rejection above 99.9 % and stable performance over 24 h. This work provides an effective pathway for designing high-flux ceramic membranes for MD.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125055"},"PeriodicalIF":9.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787092","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 : 2025-12-11DOI: 10.1016/j.memsci.2025.125053
Qiang Li , Jiaqi Han , Saisai Li , Li Zhao , Qi Zhang , Shuyun Zheng , Dongjun Lv , Fucheng Wang , Huining Deng
Dually charged Janus nanofiltration (NF) membrane strongly breaks through the limitations of traditional polyamide-based membranes in indiscriminately removing divalent anions and cations. This report successfully constructs a high-performance quaternized polyethylenimine/lignin-polyamide (QPEI/PAL) composite NF membrane by the following strategy. Firstly, a highly negatively charged PAL separation layer on a polysulfone substrate is obtained by interfacial polymerization employing piperazine/alkaline lignin as an aqueous mixture and trimesoyl chloride (TMC) as an organic solution. Then, a loose upper surface of PEI polymer is constructed on the freshly formed PAL lower surface through a reaction with the residual acyl chloride groups. Subsequently, the amine and imine groups of the PEI upper surface are transformed into quaternary ammonium ions by CH3I fumigation. The experimental results show the obtained membrane shows high pure water permeance (11.0 L m−2 h−1 bar−1) and outstanding removal for various single-divalent salts (92.6 % for Na2SO4, 98.4 % for MgCl2, 97.0 % for CaCl2, etc.). It also possesses excellent separation selectivities for NaCl/Na2SO4 (81.7) and LiCl/MgCl2 (46.9) mixtures. Even under a high Mg2+/Li+ mass ratio of 80, the corresponding Li+/Mg2+ selectivity can still reach 43.0. The abundant negative charges on the PAL lower surface facilitates the rapid diffusion of Li+ ions within the Janus separation layer. This characteristic indicates the membrane shows outstanding Li+/Mg2+ separation capability. Furthermore, compared with the pristine polyamide NF membrane, the fabricated QPEI/PAL membrane exhibits an excellent hardness removal performance for various simulated hard waters with complex compositions. Additionally, the membrane exhibits high antibacterial properties and stable separation performance for Na2SO4 and MgCl2 removal in a long-term running (168 h).
双荷电Janus纳滤膜强有力地突破了传统聚酰胺基膜不加区分地去除二价阴离子和阳离子的局限性。本文采用以下策略成功构建了高性能季铵化聚乙烯亚胺/木质素聚酰胺（QPEI/PAL）复合纳滤膜。首先，以哌嗪/碱性木质素为水溶液，三甲基氯（TMC）为有机溶液，通过界面聚合在聚砜基底上获得了高负电荷的PAL分离层。然后，通过与残留的酰氯基团反应，在新形成的PAL下表面上构建松散的PEI聚合物上表面。随后，PEI上表面的胺基和亚胺基通过CH3I熏蒸转化为季铵离子。实验结果表明，所制备的膜具有较高的纯水渗透率（11.0 L m−2 h−1 bar−1）和对各种单二价盐的去除率（Na2SO4去除率92.6%，MgCl2去除率98.4%，CaCl2去除率97.0%等）。它对NaCl/Na2SO4（81.7）和LiCl/MgCl2（46.9）混合物也有很好的分离选择性。即使在Mg2+/Li+质量比高达80的情况下，相应的Li+/Mg2+选择性仍可达到43.0。PAL下表面丰富的负电荷有利于Li+离子在Janus分离层内的快速扩散。这一特性表明该膜具有优异的Li+/Mg2+分离能力。此外，与原始聚酰胺纳滤膜相比，制备的QPEI/PAL膜对各种复杂成分的模拟硬水具有优异的去除硬度性能。此外，该膜具有较高的抗菌性能和稳定的分离性能，可以长期运行（168 h）去除Na2SO4和MgCl2。
{"title":"Dually charged quaternized PEI/lignin-polyamide composite nanofiltration membrane toward highly efficient di-/monovalent ion separation","authors":"Qiang Li , Jiaqi Han , Saisai Li , Li Zhao , Qi Zhang , Shuyun Zheng , Dongjun Lv , Fucheng Wang , Huining Deng","doi":"10.1016/j.memsci.2025.125053","DOIUrl":"10.1016/j.memsci.2025.125053","url":null,"abstract":"<div><div>Dually charged Janus nanofiltration (NF) membrane strongly breaks through the limitations of traditional polyamide-based membranes in indiscriminately removing divalent anions and cations. This report successfully constructs a high-performance quaternized polyethylenimine/lignin-polyamide (QPEI/PAL) composite NF membrane by the following strategy. Firstly, a highly negatively charged PAL separation layer on a polysulfone substrate is obtained by interfacial polymerization employing piperazine/alkaline lignin as an aqueous mixture and trimesoyl chloride (TMC) as an organic solution. Then, a loose upper surface of PEI polymer is constructed on the freshly formed PAL lower surface through a reaction with the residual acyl chloride groups. Subsequently, the amine and imine groups of the PEI upper surface are transformed into quaternary ammonium ions by CH<sub>3</sub>I fumigation. The experimental results show the obtained membrane shows high pure water permeance (11.0 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>) and outstanding removal for various single-divalent salts (92.6 % for Na<sub>2</sub>SO<sub>4</sub>, 98.4 % for MgCl<sub>2</sub>, 97.0 % for CaCl<sub>2</sub>, <em>etc.</em>). It also possesses excellent separation selectivities for NaCl/Na<sub>2</sub>SO<sub>4</sub> (81.7) and LiCl/MgCl<sub>2</sub> (46.9) mixtures. Even under a high Mg<sup>2+</sup>/Li<sup>+</sup> mass ratio of 80, the corresponding Li<sup>+</sup>/Mg<sup>2+</sup> selectivity can still reach 43.0. The abundant negative charges on the PAL lower surface facilitates the rapid diffusion of Li<sup>+</sup> ions within the Janus separation layer. This characteristic indicates the membrane shows outstanding Li<sup>+</sup>/Mg<sup>2+</sup> separation capability. Furthermore, compared with the pristine polyamide NF membrane, the fabricated QPEI/PAL membrane exhibits an excellent hardness removal performance for various simulated hard waters with complex compositions. Additionally, the membrane exhibits high antibacterial properties and stable separation performance for Na<sub>2</sub>SO<sub>4</sub> and MgCl<sub>2</sub> removal in a long-term running (168 h).</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125053"},"PeriodicalIF":9.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787155","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 : 2025-12-11DOI: 10.1016/j.memsci.2025.125054
Tingting Tang , Wenyi Zhang , Yucheng Liu , Xuewei Li , Kaibo Hu , Yinhua Wan , Jiuyang Lin
Yttrium (Y), the most abundant heavy rare earth element (HREE) in ion-adsorption type rare earth ores (IATREO), is essential for various innovative functional materials. This study employed hollow fiber renewal liquid membrane (HFRLM) technology combined with a novel phosphorus-containing extractant Cextrant322 (C322) to establish a C322-HFRLM system for the selective separation of Y3+ from Y-rich HREEs solution of IATREO. Under the optimized conditions of 0.5 mol L−1 C322, feed phase pH of 3, flow rate of 550 mL min−1, and stripping-to-feed volume ratio (VS/VF) of 1.6, the results demonstrated that the purity of Y3+ in the feed phase increased from 61.90 % to 97.69 % after a single-step simultaneous extraction-stripping process. The maximum separation factor (SF) values between Ho3+-Lu3+ and Y3+ (i.e., SFHo/Y, SFEr/Y, SFTm/Y, SFYb/Y, and SFLu/Y) were 1.32, 2.41, 5.71, 8.60, and 9.80 at 0.25-h operation, respectively. Compared with the traditional hollow fiber supported liquid membrane (HFSLM) system, the C322-HFRLM system achieved 1.29 times increase in Y3+ purity, demonstrating significantly enhanced separation efficiency and stability. Therefore, HFRLM presents substantial potential as an advanced membrane separation technology for the efficient industrial-scale separation and enrichment of Y3+.
{"title":"Highly selective separation of yttrium from heavy rare earth elements by hollow fiber renewal liquid membrane","authors":"Tingting Tang , Wenyi Zhang , Yucheng Liu , Xuewei Li , Kaibo Hu , Yinhua Wan , Jiuyang Lin","doi":"10.1016/j.memsci.2025.125054","DOIUrl":"10.1016/j.memsci.2025.125054","url":null,"abstract":"<div><div>Yttrium (Y), the most abundant heavy rare earth element (HREE) in ion-adsorption type rare earth ores (IATREO), is essential for various innovative functional materials. This study employed hollow fiber renewal liquid membrane (HFRLM) technology combined with a novel phosphorus-containing extractant Cextrant322 (C322) to establish a C322-HFRLM system for the selective separation of Y<sup>3+</sup> from Y-rich HREEs solution of IATREO. Under the optimized conditions of 0.5 mol L<sup>−1</sup> C322, feed phase pH of 3, flow rate of 550 mL min<sup>−1</sup>, and stripping-to-feed volume ratio (<em>V</em><sub>S</sub>/<em>V</em><sub>F</sub>) of 1.6, the results demonstrated that the purity of Y<sup>3+</sup> in the feed phase increased from 61.90 % to 97.69 % after a single-step simultaneous extraction-stripping process. The maximum separation factor (<em>SF</em>) values between Ho<sup>3+</sup>-Lu<sup>3+</sup> and Y<sup>3+</sup> (i.e., <em>SF</em><sub>Ho/Y</sub>, <em>SF</em><sub>Er/Y</sub>, <em>SF</em><sub>Tm/Y</sub>, <em>SF</em><sub>Yb/Y</sub>, and <em>SF</em><sub>Lu/Y</sub>) were 1.32, 2.41, 5.71, 8.60, and 9.80 at 0.25-h operation, respectively. Compared with the traditional hollow fiber supported liquid membrane (HFSLM) system, the C322-HFRLM system achieved 1.29 times increase in Y<sup>3+</sup> purity, demonstrating significantly enhanced separation efficiency and stability. Therefore, HFRLM presents substantial potential as an advanced membrane separation technology for the efficient industrial-scale separation and enrichment of Y<sup>3+</sup>.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125054"},"PeriodicalIF":9.0,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734430","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 : 2025-12-10DOI: 10.1016/j.memsci.2025.125040
Junkai Gong , Zhiwei Zhou , Hao Wang , Chuang Lei , Qiangqiang Yang , Xiaoguang Wang , Lu Shao , Yanqiu Zhang
Covalent organic framework (COF)-based membranes exhibit exceptional potential for molecular separation owing to their well-defined nanoporosity, tailorable pore apertures, and high surface-to-volume ratios. However, achieving precise pore-size regulation remains a critical challenge in membrane design. Herein, we report a defect-engineering strategy for COF membranes through in-situ polydopamine (PDA) incorporation during interfacial polymerization. Dopamine undergoes oxidative self-polymerization in the p-phenylenediamine (Pa) aqueous phase, generating PDA that simultaneously reacts with Pa monomers and infiltrates TpPa-COF framework defects via Schiff-base chemistry. This dual-function modification not only repairs structural imperfections, but also introduces hydrophilic moieties that enhance surface wettability. The optimized PDA-TpPa membrane demonstrates superior separation performance, achieving 99 % rejection of organic dyes while maintaining a high water permeance of 117.3 L m−2 h−1 bar−1. Furthermore, the membrane exhibits considerable permeance towards various organic solvents, notably for n-hexane, which reached as high as 337 L m−2 h−1 bar−1. This work establishes a novel paradigm for fabricating high-performance COF membranes.
共价有机骨架（COF）基膜由于具有明确的纳米孔隙度、可定制的孔径和高表面体积比，表现出非凡的分子分离潜力。然而，实现精确的孔径调节仍然是膜设计中的一个关键挑战。在此，我们报告了在界面聚合过程中通过原位聚多巴胺（PDA）掺入COF膜的缺陷工程策略。多巴胺在对苯二胺（Pa）水相中进行氧化自聚合，生成PDA，该PDA同时与Pa单体反应，并通过希夫碱化学渗透TpPa-COF框架缺陷。这种双重功能的修饰不仅修复了结构缺陷，而且还引入了增强表面润湿性的亲水部分。优化后的PDA-TpPa膜具有优异的分离性能，对有机染料的去除率达到99%，同时保持了117.3 L m−2 h−1 bar−1的高透水性。此外，该膜对各种有机溶剂表现出相当大的渗透性，特别是对正己烷，其渗透性高达337 L m−2 h−1 bar−1。这项工作为制造高性能碳纤维膜建立了一个新的范例。
{"title":"Molecular welded interface engineering to synthesize covalent organic framework membranes for ultrafast molecular sieving","authors":"Junkai Gong , Zhiwei Zhou , Hao Wang , Chuang Lei , Qiangqiang Yang , Xiaoguang Wang , Lu Shao , Yanqiu Zhang","doi":"10.1016/j.memsci.2025.125040","DOIUrl":"10.1016/j.memsci.2025.125040","url":null,"abstract":"<div><div>Covalent organic framework (COF)-based membranes exhibit exceptional potential for molecular separation owing to their well-defined nanoporosity, tailorable pore apertures, and high surface-to-volume ratios. However, achieving precise pore-size regulation remains a critical challenge in membrane design. Herein, we report a defect-engineering strategy for COF membranes through in-situ polydopamine (PDA) incorporation during interfacial polymerization. Dopamine undergoes oxidative self-polymerization in the <em>p</em>-phenylenediamine (Pa) aqueous phase, generating PDA that simultaneously reacts with Pa monomers and infiltrates TpPa-COF framework defects via Schiff-base chemistry. This dual-function modification not only repairs structural imperfections, but also introduces hydrophilic moieties that enhance surface wettability. The optimized PDA-TpPa membrane demonstrates superior separation performance, achieving 99 % rejection of organic dyes while maintaining a high water permeance of 117.3 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>. Furthermore, the membrane exhibits considerable permeance towards various organic solvents, notably for n-hexane, which reached as high as 337 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>. This work establishes a novel paradigm for fabricating high-performance COF membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125040"},"PeriodicalIF":9.0,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787153","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 : 2025-12-10DOI: 10.1016/j.memsci.2025.125050
Lei Huang , Xueting Zhao , Jinmao Lv , Xinliang Zhang , Zhihong Dong , Anqi Liu , Jiefeng Pan , Xiaocheng Lin
Controllable assembly of covalent organic framework (COF) nanosheets into two-dimensional (2D) layered membranes is crucial to prepare advanced membranes. However, the prevalence of disordered stacking of COF nanosheets often leads to tortuous or overlapped pores and sacrifices membrane permeability. Further, membrane stability is often questioned due to weak interlayer interactions. Herein, a three-dimensional (3D) polyphenol-mediated interlayer engineering strategy was proposed for manipulating the interlayer channels and interactions of COF membranes for simultaneous enhancement of membrane permeability and stability. The COF membranes (TTSBI/TFTA-TG(Cl)) were prepared via vacuum-assisted self-assembly method with TFTA-TG(Cl) COF nanosheets as the building host and 3D polyphenols 5,5′,6,6′-Tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane (TTSBI) as intercalating guests. The stereoscopic spirocyclic architecture of TTSBI provides rigid interlayer support to expand the 2D nanochannels within the COF membranes, which optimizes the water molecule transport pathway to enhance water permeance. The multiple interactions (e.g., electrostatic and cation-π interactions) between TTSBI and COF nanosheets strengthen the interlayer combination, thereby enhancing the structural stability of the COF membrane. The as-prepared TTSBI/TFTA-TG(Cl) membrane exhibited water permeance of 77.3 L m−2 h−1·bar−1 (approximately 2.5 times that of the pristine TFTA-TG(Cl) membrane) with methylene blue rejection above 91 %. Furthermore, the TTSBI/TFTA-TG(Cl) membrane can effectively reject dye molecules with molecular weight of ≥800 Da, and simultaneously demonstrate superior stability. This polyphenol-mediated interlayer engineering strategy may provide new insights into the construction and manipulation of the channels in COF membranes for high-permeability separation application.
{"title":"3D polyphenol-intercalated covalent organic framework membranes: Toward interlayer manipulation for high-permeability nanofiltration","authors":"Lei Huang , Xueting Zhao , Jinmao Lv , Xinliang Zhang , Zhihong Dong , Anqi Liu , Jiefeng Pan , Xiaocheng Lin","doi":"10.1016/j.memsci.2025.125050","DOIUrl":"10.1016/j.memsci.2025.125050","url":null,"abstract":"<div><div>Controllable assembly of covalent organic framework (COF) nanosheets into two-dimensional (2D) layered membranes is crucial to prepare advanced membranes. However, the prevalence of disordered stacking of COF nanosheets often leads to tortuous or overlapped pores and sacrifices membrane permeability. Further, membrane stability is often questioned due to weak interlayer interactions. Herein, a three-dimensional (3D) polyphenol-mediated interlayer engineering strategy was proposed for manipulating the interlayer channels and interactions of COF membranes for simultaneous enhancement of membrane permeability and stability. The COF membranes (TTSBI/TFTA-TG<sub>(Cl)</sub>) were prepared via vacuum-assisted self-assembly method with TFTA-TG<sub>(Cl)</sub> COF nanosheets as the building host and 3D polyphenols 5,5′,6,6′-Tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane (TTSBI) as intercalating guests. The stereoscopic spirocyclic architecture of TTSBI provides rigid interlayer support to expand the 2D nanochannels within the COF membranes, which optimizes the water molecule transport pathway to enhance water permeance. The multiple interactions (e.g., electrostatic and cation-π interactions) between TTSBI and COF nanosheets strengthen the interlayer combination, thereby enhancing the structural stability of the COF membrane. The as-prepared TTSBI/TFTA-TG<sub>(Cl)</sub> membrane exhibited water permeance of 77.3 L m<sup>−2</sup> h<sup>−1</sup>·bar<sup>−1</sup> (approximately 2.5 times that of the pristine TFTA-TG<sub>(Cl)</sub> membrane) with methylene blue rejection above 91 %. Furthermore, the TTSBI/TFTA-TG<sub>(Cl)</sub> membrane can effectively reject dye molecules with molecular weight of ≥800 Da, and simultaneously demonstrate superior stability. This polyphenol-mediated interlayer engineering strategy may provide new insights into the construction and manipulation of the channels in COF membranes for high-permeability separation application.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125050"},"PeriodicalIF":9.0,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734326","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 : 2025-12-09DOI: 10.1016/j.memsci.2025.125019
Jinmao Lv , Xueting Zhao , Lei Huang , Xuexi Zhang , Yu Sun , Jiefeng Pan , Xiaocheng Lin
Electrodialysis technology, an energy-efficient membrane separation technique, relies on the performance of its core component—ion exchange membranes (IEMs). However, anion exchange membranes (AEMs) still lag behind cation exchange membranes (CEMs, e.g., Nafion), primarily due to the trade-off between minimizing area resistance and maintaining dimensional stability. To tackle this issue, we leveraged 1-vinylimidazole (1-VIm) as a dual-functional agent by grafting it onto chloromethylated polysulfone (CMPSF) via N-alkylation and subsequently employing its vinyl group for in-situ self-polymerization to form the crosslinked structure. Results demonstrate that the 1-VIm self-crosslinked structure enables the coexistence of a high ion exchange capacity (IEC) for low area resistance and outstanding dimensional stability (suppressed swelling). The optimal VIPSF-3 membrane exhibits a swelling ratio of only 8.0 ± 0.5 % at 60 °C, while significantly enhancing membrane selectivity with an ion transport number () as high as 0.990 ± 0.002. During a 140-min electrodialysis desalination test, the optimized VIPSF-3 membrane outperformed the commercial AMV AEM by achieving a salt removal rate () of 90.5 ± 0.8 %, a current efficiency (η) of 98.3 ± 0.8 %, and an energy consumption (EC) of 4.04 ± 0.13 kWh·kg−1. These values surpass those of AMV ( = 82.4 ± 1.0 %, η = 88.3 ± 1.1 %, EC = 5.20 ± 0.17 kWh·kg−1). This study provides a novel strategy for preparing high-performance AEMs for electrodialysis applications.
{"title":"Preparation of polysulfone-based imidazole-functionalized self-crosslinked anion exchange membranes for electrodialysis","authors":"Jinmao Lv , Xueting Zhao , Lei Huang , Xuexi Zhang , Yu Sun , Jiefeng Pan , Xiaocheng Lin","doi":"10.1016/j.memsci.2025.125019","DOIUrl":"10.1016/j.memsci.2025.125019","url":null,"abstract":"<div><div>Electrodialysis technology, an energy-efficient membrane separation technique, relies on the performance of its core component—ion exchange membranes (IEMs). However, anion exchange membranes (AEMs) still lag behind cation exchange membranes (CEMs, e.g., Nafion), primarily due to the trade-off between minimizing area resistance and maintaining dimensional stability. To tackle this issue, we leveraged 1-vinylimidazole (1-VIm) as a dual-functional agent by grafting it onto chloromethylated polysulfone (CMPSF) via N-alkylation and subsequently employing its vinyl group for in-situ self-polymerization to form the crosslinked structure. Results demonstrate that the 1-VIm self-crosslinked structure enables the coexistence of a high ion exchange capacity (<em>IEC</em>) for low area resistance and outstanding dimensional stability (suppressed swelling). The optimal VIPSF-3 membrane exhibits a swelling ratio of only 8.0 ± 0.5 % at 60 °C, while significantly enhancing membrane selectivity with an ion transport number (<span><math><mrow><msub><mi>t</mi><mi>i</mi></msub></mrow></math></span>) as high as 0.990 ± 0.002. During a 140-min electrodialysis desalination test, the optimized VIPSF-3 membrane outperformed the commercial AMV AEM by achieving a salt removal rate (<span><math><mrow><msub><mi>R</mi><mrow><mi>s</mi><mi>a</mi><mi>l</mi><mi>t</mi></mrow></msub></mrow></math></span>) of 90.5 ± 0.8 %, a current efficiency (<em>η</em>) of 98.3 ± 0.8 %, and an energy consumption (<em>EC</em>) of 4.04 ± 0.13 kWh·kg<sup>−1</sup>. These values surpass those of AMV (<span><math><mrow><msub><mi>R</mi><mrow><mi>s</mi><mi>a</mi><mi>l</mi><mi>t</mi></mrow></msub></mrow></math></span> = 82.4 ± 1.0 %, <em>η</em> = 88.3 ± 1.1 %, <em>EC</em> = 5.20 ± 0.17 kWh·kg<sup>−1</sup>). This study provides a novel strategy for preparing high-performance AEMs for electrodialysis applications.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125019"},"PeriodicalIF":9.0,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734434","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 : 2025-12-09DOI: 10.1016/j.memsci.2025.125039
Daria Syrtsova , Alexandr Zinoviev , Alyona Wozniak , Maxim Bermeshev , Elena Skryleva , Roman Nikiforov , Mikhail Piskarev , Alexander Кuznetsov , Alexandr Alentiev , Alla Gilman , Victoria Ryzhikh
Low-temperature plasma treatment is demonstrated as an effective strategy to enhance the gas separation performance of a vinyl-addition polymer synthesized from the industrially available monomer 5-ethylidene-2-norbornene (APENB). The plasma modification introduces controlled surface and near-surface functionalities without compromising the bulk integrity of the polymer matrix. Structural and physicochemical analyses (XPS, FTIR, AFM) confirmed the incorporation of polar functional groups into the surface layer, resulting in a significantly improved permeability–selectivity balance. A systematic investigation of air plasma treatment conditions revealed the optimal parameters for enhancing gas transport performance. A 30-s plasma exposure was found to be optimal, yielding a more than twofold increase in O2/N2 selectivity and over a 20-fold enhancement in He/CH4 and H2/CH4 selectivity. Aging studies over a one-month period showed that the improved transport properties remained stable, with the H2/CH4 performance of treated polymer exceeding the 2015 Robeson upper bound. This work highlights the potential of plasma-based surface engineering to unlock advanced transport properties in commercially viable membrane materials for industrial gas separation.
{"title":"Advancing gas separation performance: Plasma-treated polymer from 5-ethylidene-2-norbornene beyond the Robeson upper bound","authors":"Daria Syrtsova , Alexandr Zinoviev , Alyona Wozniak , Maxim Bermeshev , Elena Skryleva , Roman Nikiforov , Mikhail Piskarev , Alexander Кuznetsov , Alexandr Alentiev , Alla Gilman , Victoria Ryzhikh","doi":"10.1016/j.memsci.2025.125039","DOIUrl":"10.1016/j.memsci.2025.125039","url":null,"abstract":"<div><div>Low-temperature plasma treatment is demonstrated as an effective strategy to enhance the gas separation performance of a vinyl-addition polymer synthesized from the industrially available monomer 5-ethylidene-2-norbornene (APENB). The plasma modification introduces controlled surface and near-surface functionalities without compromising the bulk integrity of the polymer matrix. Structural and physicochemical analyses (XPS, FTIR, AFM) confirmed the incorporation of polar functional groups into the surface layer, resulting in a significantly improved permeability–selectivity balance. A systematic investigation of air plasma treatment conditions revealed the optimal parameters for enhancing gas transport performance. A 30-s plasma exposure was found to be optimal, yielding a more than twofold increase in O<sub>2</sub>/N<sub>2</sub> selectivity and over a 20-fold enhancement in He/CH<sub>4</sub> and H<sub>2</sub>/CH<sub>4</sub> selectivity. Aging studies over a one-month period showed that the improved transport properties remained stable, with the H<sub>2</sub>/CH<sub>4</sub> performance of treated polymer exceeding the 2015 Robeson upper bound. This work highlights the potential of plasma-based surface engineering to unlock advanced transport properties in commercially viable membrane materials for industrial gas separation.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125039"},"PeriodicalIF":9.0,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734432","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 : 2025-12-09DOI: 10.1016/j.memsci.2025.125045
Zitong Huang , Kai wang , Ruofei Gao , Yi Cheng , Xinxin Li , Jinhua Ji , Xiaomeng Chu , Shaojie Liu , Nanwen Li
Ion-solvating membranes (ISMs) with high ionic conductivity and robust chemical stability are essential for high-performance alkaline water electrolysis (AWE). While naphthalene-based polybenzimidazoles (NPBI) demonstrate promising stability, their OH− conductivity remains limited due to insufficient electrolyte uptake and poorly organized ion transport pathways. To address this limitation, we developed a series of branched NPBI copolymers (NPBI-BM-x) through strategic incorporation of rigid tricarboxylic acid comonomers. This molecular design introduces rigid or articulated branching centers that disrupt chain packing and generate uniformly and continuously distributed ultra-micropores (0.54–0.58 nm), as confirmed by CO2 adsorption, XRD, and simulation. The tailored ultra-microporosity provide large free volume within the membrane, which significantly enhancing KOH absorption and facilitating rapid hydroxide transport. The optimized membrane NPBI-BM2-6 achieves a KOH uptake of 99.8 wt% and an OH− conductivity of 225 mS/cm at 80 °C in 6 M KOH which is 1.9 times higher than that of the linear NPBI. When integrated into an AWE cell with non-noble catalysts, the membrane enables a current density of 2.5 A/cm2 at 2.0 V and 80 °C (even achieved 3.58 A/cm2 90 °C) and voltage remained stable in a 685 h test. This branched ultra-microporous molecularly engineered architecture unlocks durable, high-performance alkaline water electrolysis.
离子溶剂化膜（ISMs）具有高离子电导率和强大的化学稳定性，是高性能碱性电解（AWE）的必要条件。虽然萘基多苯并咪唑（NPBI）表现出良好的稳定性，但由于电解质摄取不足和离子运输途径组织不良，它们的OH -电导率仍然有限。为了解决这一限制，我们通过战略性地加入刚性三羧酸共聚物，开发了一系列支链NPBI共聚物（NPBI- bm -x）。这种分子设计引入了刚性或铰接的分支中心，破坏了链式包装，产生了均匀连续分布的超微孔（0.54-0.58 nm），这一点得到了CO2吸附、XRD和模拟的证实。定制的超微孔提供了大的膜内自由体积，显著增强了KOH的吸收，促进了氢氧化物的快速运输。优化后的NPBI- bm2 -6膜的KOH吸收率为99.8 wt%，在80°C、6 M KOH条件下的OH -电导率为225 mS/cm，是线性NPBI膜的1.9倍。当与非贵金属催化剂集成到AWE电池中时，该膜在2.0 V和80°C时的电流密度为2.5 a /cm2(90°C时甚至达到3.58 a /cm2)，并且在685小时的测试中电压保持稳定。这种分支的超微孔分子工程结构开启了持久、高性能的碱性电解。
{"title":"Ultra-microporosity enabled by the branched polybenzimidazole ion-solvating membranes for high performance alkaline water electrolysis","authors":"Zitong Huang , Kai wang , Ruofei Gao , Yi Cheng , Xinxin Li , Jinhua Ji , Xiaomeng Chu , Shaojie Liu , Nanwen Li","doi":"10.1016/j.memsci.2025.125045","DOIUrl":"10.1016/j.memsci.2025.125045","url":null,"abstract":"<div><div>Ion-solvating membranes (ISMs) with high ionic conductivity and robust chemical stability are essential for high-performance alkaline water electrolysis (AWE). While naphthalene-based polybenzimidazoles (NPBI) demonstrate promising stability, their OH<sup>−</sup> conductivity remains limited due to insufficient electrolyte uptake and poorly organized ion transport pathways. To address this limitation, we developed a series of branched NPBI copolymers (NPBI-BM-x) through strategic incorporation of rigid tricarboxylic acid comonomers. This molecular design introduces rigid or articulated branching centers that disrupt chain packing and generate uniformly and continuously distributed ultra-micropores (0.54–0.58 nm), as confirmed by CO<sub>2</sub> adsorption, XRD, and simulation. The tailored ultra-microporosity provide large free volume within the membrane, which significantly enhancing KOH absorption and facilitating rapid hydroxide transport. The optimized membrane NPBI-BM<sub>2</sub>-6 achieves a KOH uptake of 99.8 wt% and an OH<sup>−</sup> conductivity of 225 mS/cm at 80 °C in 6 M KOH which is 1.9 times higher than that of the linear NPBI. When integrated into an AWE cell with non-noble catalysts, the membrane enables a current density of 2.5 A/cm<sup>2</sup> at 2.0 V and 80 °C (even achieved 3.58 A/cm<sup>2</sup> 90 °C) and voltage remained stable in a 685 h test. This branched ultra-microporous molecularly engineered architecture unlocks durable, high-performance alkaline water electrolysis.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125045"},"PeriodicalIF":9.0,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734436","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}
Mixed matrix membranes (MMMs) have emerged as a critical platform for molecular separation, especially carbon capture from point-emission sources. In this study, a series of novel MMMs were fabricated by incorporating the bimetallic Ag/Zn-ZIF-8 nanoparticles into the poly (ether-block-amide) (Pebax) matrix for efficient CO2/N2 separation. The SEM, EDS, XRD, FTIR, XPS, TGA, N2 adsorption-desorption measurements were employed to elucidate the microstructures and physicochemical properties of the resultant nanoparticles and membranes. The bimetallic coordination-induced optimization modulated the inherent structure of ZIF-8 framework and enhanced CO2 affinity, thereby forming the CO2-selective transport channels over N2. The incorporation of Ag + promoted the uniform dispersion of Ag/Zn-ZIF-8 nanoparticles in Pebax matrix, indicating the excellent polymer-filler interfacial compatibility. Impressively, the resulting membrane achieved the superior separation performance with a CO2 permeability of 359 Barrer and a CO2/N2 selectivity of 53, which were 2.5 and 1.4 times higher than that of the pristine Pebax membrane. Besides, the introduction of Ag/Zn-ZIF-8 nanoparticles enhanced the thermal and mechanical stability of the membrane, ensuring the potential for long-term operation. These findings herein advance the rational design and preparation of high-performance MMMs for sustainable carbon capture.
{"title":"Bimetallic engineering in Ag/Zn-ZIF-8/Pebax mixed matrix membranes for enhanced CO2 separation","authors":"Qian-Qian Li, Yang Li, Heng Mao, Yan-Mei Zhang, Qiu-Ying Zhang, Xin-Ru Chen, Zi-Cong Shan, Xian-Zhe Zhou, Li-Hao Xu, Zhi-Ping Zhao","doi":"10.1016/j.memsci.2025.125046","DOIUrl":"10.1016/j.memsci.2025.125046","url":null,"abstract":"<div><div>Mixed matrix membranes (MMMs) have emerged as a critical platform for molecular separation, especially carbon capture from point-emission sources. In this study, a series of novel MMMs were fabricated by incorporating the bimetallic Ag/Zn-ZIF-8 nanoparticles into the poly (ether-block-amide) (Pebax) matrix for efficient CO<sub>2</sub>/N<sub>2</sub> separation. The SEM, EDS, XRD, FTIR, XPS, TGA, N<sub>2</sub> adsorption-desorption measurements were employed to elucidate the microstructures and physicochemical properties of the resultant nanoparticles and membranes. The bimetallic coordination-induced optimization modulated the inherent structure of ZIF-8 framework and enhanced CO<sub>2</sub> affinity, thereby forming the CO<sub>2</sub>-selective transport channels over N<sub>2</sub>. The incorporation of Ag <sup>+</sup> promoted the uniform dispersion of Ag/Zn-ZIF-8 nanoparticles in Pebax matrix, indicating the excellent polymer-filler interfacial compatibility. Impressively, the resulting membrane achieved the superior separation performance with a CO<sub>2</sub> permeability of 359 Barrer and a CO<sub>2</sub>/N<sub>2</sub> selectivity of 53, which were 2.5 and 1.4 times higher than that of the pristine Pebax membrane. Besides, the introduction of Ag/Zn-ZIF-8 nanoparticles enhanced the thermal and mechanical stability of the membrane, ensuring the potential for long-term operation. These findings herein advance the rational design and preparation of high-performance MMMs for sustainable carbon capture.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125046"},"PeriodicalIF":9.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734324","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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