Pub Date : 2025-11-24DOI: 10.1016/j.advmem.2025.100190
Zhangjun Dai , Pei Nian , Longtian Cao , Xiaolong Wang , Xinhua Gao , Wenlan Ji , Yibin Wei
Catalytic conversion of CO2 into high value-added chemicals offers an attractive route to address a range of climate issues caused by excessive CO2 emission. However, the chemical inertness of CO2 generally leads to unsatisfied CO2 conversion and product selectivity. Catalytic membrane reactors (CMRs) have been considered promising to break the thermodynamic equilibrium of CO2 catalytic reactions. This review firstly provides an overview of chemical reactions utilizing CO2 and the classification of potential CO2-derived chemical products. Then, the fundamentals of catalytic CO2 conversion and the analysis of opportunities and difficulties of such reactions are presented. The advances of microporous membrane-based CMRs are deeply discussed regarding the membrane materials, applications for common chemical synthesis and reactor designs. Finally, the current achievements and future outlook in microporous membrane reactors (MMRs) for CO2 catalytic conversion are summarized.
{"title":"Recent progress in microporous membrane reactors for catalytic conversion CO2 into value-added chemicals","authors":"Zhangjun Dai , Pei Nian , Longtian Cao , Xiaolong Wang , Xinhua Gao , Wenlan Ji , Yibin Wei","doi":"10.1016/j.advmem.2025.100190","DOIUrl":"10.1016/j.advmem.2025.100190","url":null,"abstract":"<div><div>Catalytic conversion of CO<sub>2</sub> into high value-added chemicals offers an attractive route to address a range of climate issues caused by excessive CO<sub>2</sub> emission. However, the chemical inertness of CO<sub>2</sub> generally leads to unsatisfied CO<sub>2</sub> conversion and product selectivity. Catalytic membrane reactors (CMRs) have been considered promising to break the thermodynamic equilibrium of CO<sub>2</sub> catalytic reactions. This review firstly provides an overview of chemical reactions utilizing CO<sub>2</sub> and the classification of potential CO<sub>2</sub>-derived chemical products. Then, the fundamentals of catalytic CO<sub>2</sub> conversion and the analysis of opportunities and difficulties of such reactions are presented. The advances of microporous membrane-based CMRs are deeply discussed regarding the membrane materials, applications for common chemical synthesis and reactor designs. Finally, the current achievements and future outlook in microporous membrane reactors (MMRs) for CO<sub>2</sub> catalytic conversion are summarized.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"7 ","pages":"Article 100190"},"PeriodicalIF":9.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748835","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-06DOI: 10.1016/j.advmem.2025.100188
Jingsi Yuan , Keke Liu , Yunqiu Zhou , Penglin Cheng , Binyu Zhou , Xueli Cao , Miaomiao Tian , Shi-Peng Sun , Yatao Zhang , Junyong Zhu
Covalent organic frameworks (COFs), which are porous crystalline materials built using reticular and dynamic covalent chemistry, are attracting significant interest in advanced membrane separations. Their appeal stems from their higher mass transport efficiency and superior precision sieving, enabled by their ordered and modifiable pore channels, high porosity, and designable structure. Hydrazone-linked COFs, a subclass of Schiff base COFs, have emerged as promising membrane materials due to their large surface area, structural flexibility, and abundant heteroatomic sites. The versatility of their structure allows for precise tuning of pore size, architecture, and functionality by selecting specific building blocks or through post-modification, enabling the development of customized membranes for targeted separations. This review provides a comprehensive examination of the synthesis methods and applications of hydrazone-linked COF-based membranes, highlighting how their chemical stability, pore characteristics, and heteroatomic functionalities govern their performance. We analyze various fabrication techniques—including mixing, interfacial polymerization, covalent nanosheet stacking, and in situ growth—and discuss their impact on membrane performance. The applications in gas separation, water treatment, membrane catalysis, and energy storage are systematically evaluated, with a comparative analysis against conventional membrane materials. Finally, we identify persistent challenges related to scalability and long-term stability and outline future research directions to facilitate the practical implementation of these advanced membranes.
{"title":"Hydrazone-linked covalent organic frameworks for membrane separation","authors":"Jingsi Yuan , Keke Liu , Yunqiu Zhou , Penglin Cheng , Binyu Zhou , Xueli Cao , Miaomiao Tian , Shi-Peng Sun , Yatao Zhang , Junyong Zhu","doi":"10.1016/j.advmem.2025.100188","DOIUrl":"10.1016/j.advmem.2025.100188","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs), which are porous crystalline materials built using reticular and dynamic covalent chemistry, are attracting significant interest in advanced membrane separations. Their appeal stems from their higher mass transport efficiency and superior precision sieving, enabled by their ordered and modifiable pore channels, high porosity, and designable structure. Hydrazone-linked COFs, a subclass of Schiff base COFs, have emerged as promising membrane materials due to their large surface area, structural flexibility, and abundant heteroatomic sites. The versatility of their structure allows for precise tuning of pore size, architecture, and functionality by selecting specific building blocks or through post-modification, enabling the development of customized membranes for targeted separations. This review provides a comprehensive examination of the synthesis methods and applications of hydrazone-linked COF-based membranes, highlighting how their chemical stability, pore characteristics, and heteroatomic functionalities govern their performance. We analyze various fabrication techniques—including mixing, interfacial polymerization, covalent nanosheet stacking, and <em>in situ</em> growth—and discuss their impact on membrane performance. The applications in gas separation, water treatment, membrane catalysis, and energy storage are systematically evaluated, with a comparative analysis against conventional membrane materials. Finally, we identify persistent challenges related to scalability and long-term stability and outline future research directions to facilitate the practical implementation of these advanced membranes.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100188"},"PeriodicalIF":9.5,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-05DOI: 10.1016/j.advmem.2025.100187
Fan Liu , Xin Wang , Jun Wu , Hongbo Yang , Baolong Li , Zihui Dong , Xutong Han , Xiaolei Li , Qinglin Huang
The efficient separation of emulsion and the simultaneous degradation of organic pollutants remain critical challenges in wastewater treatment, particularly under harsh environments. In this work, a multifunctional Polytetrafluoroethylene (PTFE)/β-FeOOH (beta-iron oxyhydroxide) nanofiber membrane was successfully fabricated via electrospinning combined with in situ mineralization. The membrane exhibited superamphiphilicity in air, underwater superoleophobicity, and superhydrophobicity in oil, with tunable surface wettability. Uniformly anchored β-FeOOH nanorods increased surface roughness and hydrophilicity while providing abundant catalytic sites, enabling synergistic oil–water emulsion separation and photo-Fenton degradation. At a low operating pressure of 0.2 bar, high permeation fluxes of 2713.29 and 2108.37 L·m⁻²·h⁻¹ were achieved for O/W (oil in water) and W/O(water in oil) emulsions, with separation efficiencies up to 99.90 %. The membrane maintained excellent chemical stability after 10 separation–regeneration cycles under pH 1 and 30 wt% NaOH conditions, retaining fluxes of 1948.47 and 2150.53 L·m⁻²·h⁻¹ with efficiencies of 99.38 % and 99.62 %, respectively. Additionally, methylene blue (MB) and rhodamine B (Rh B) removal rates remained above 98 % after five photo-Fenton cycles, and the flux recovery rate reached 97.88 %. These results demonstrate superior chemical resistance, antifouling properties, and long-term durability. Therefore, the proposed PTFE/β-FeOOH nanofiber membrane offers a promising strategy for efficient emulsion separation and organic pollutant purification in harsh environments.
{"title":"A novel homogeneous amphipathic PTFE/β-FeOOH nanofiber membrane for emulsion separation and photocatalytic degradation in harsh environments","authors":"Fan Liu , Xin Wang , Jun Wu , Hongbo Yang , Baolong Li , Zihui Dong , Xutong Han , Xiaolei Li , Qinglin Huang","doi":"10.1016/j.advmem.2025.100187","DOIUrl":"10.1016/j.advmem.2025.100187","url":null,"abstract":"<div><div>The efficient separation of emulsion and the simultaneous degradation of organic pollutants remain critical challenges in wastewater treatment, particularly under harsh environments. In this work, a multifunctional Polytetrafluoroethylene (PTFE)/β-FeOOH (beta-iron oxyhydroxide) nanofiber membrane was successfully fabricated via electrospinning combined with in situ mineralization. The membrane exhibited superamphiphilicity in air, underwater superoleophobicity, and superhydrophobicity in oil, with tunable surface wettability. Uniformly anchored β-FeOOH nanorods increased surface roughness and hydrophilicity while providing abundant catalytic sites, enabling synergistic oil–water emulsion separation and photo-Fenton degradation. At a low operating pressure of 0.2 bar, high permeation fluxes of 2713.29 and 2108.37 L·m⁻²·h⁻¹ were achieved for O/W (oil in water) and W/O(water in oil) emulsions, with separation efficiencies up to 99.90 %. The membrane maintained excellent chemical stability after 10 separation–regeneration cycles under pH 1 and 30 wt% NaOH conditions, retaining fluxes of 1948.47 and 2150.53 L·m⁻²·h⁻¹ with efficiencies of 99.38 % and 99.62 %, respectively. Additionally, methylene blue (MB) and rhodamine B (Rh B) removal rates remained above 98 % after five photo-Fenton cycles, and the flux recovery rate reached 97.88 %. These results demonstrate superior chemical resistance, antifouling properties, and long-term durability. Therefore, the proposed PTFE/β-FeOOH nanofiber membrane offers a promising strategy for efficient emulsion separation and organic pollutant purification in harsh environments.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100187"},"PeriodicalIF":9.5,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145529066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-03DOI: 10.1016/j.advmem.2025.100186
Yi Gao , Tengpeng Wang , Fangsheng Liu , Dongjie Fan , Xiaoyu Xie , Zhengmao Ye , Dehua Dong , Huanting Wang , Zongping Shao
Ceramic oxygen separation membranes have advantages over cryogenic distillation and pressure swing adsorption in terms of oxygen production. However, the application of ceramic membranes is restricted by membrane stability issues at high operation temperatures. This study develops ultra-stable oxygen separation membranes through the over-doping of Ni into yttrium-doped zirconia (NYSZ). The Ni doping amount reaches 18.1 mol%, and Ni dissolution substantially increases the electronic conductivity of the yttrium-doped zirconia membranes under both oxidizing and reducing atmospheres, which is as high as 0.96 S cm−1. Accordingly, high oxygen permeation rates of up to 1.68 mL min−1 cm−2 at 800 °C were achieved, which are comparable with those of conventional perovskite membranes (3.53 mL min−1 cm−2). The ultra-stable NYSZ membranes were confirmed with stable electrochemical reforming of methane for 310 h. Therefore, the robust NYSZ membranes demonstrate great potential in practical applications.
在制氧方面，陶瓷氧分离膜具有低温蒸馏和变压吸附的优点。然而，陶瓷膜的应用受到高温下膜稳定性问题的限制。本研究通过在掺钇氧化锆（NYSZ）中过量掺杂Ni来制备超稳定的氧分离膜。Ni掺杂量达到18.1 mol%，在氧化和还原气氛下，Ni的溶解均显著提高了钇掺杂氧化锆膜的电导率，最高可达0.96 S cm−1。因此，在800°C下实现了高达1.68 mL min - 1 cm - 2的高氧渗透率，这与传统钙钛矿膜（3.53 mL min - 1 cm - 2）相当。通过稳定的甲烷电化学重整310 h，证实了NYSZ膜的超稳定性。因此，坚固耐用的NYSZ膜在实际应用中显示出巨大的潜力。
{"title":"Ultra-stable Ni-overdoped yttria-stabilized zirconia oxygen separation membranes for methane partial oxidation","authors":"Yi Gao , Tengpeng Wang , Fangsheng Liu , Dongjie Fan , Xiaoyu Xie , Zhengmao Ye , Dehua Dong , Huanting Wang , Zongping Shao","doi":"10.1016/j.advmem.2025.100186","DOIUrl":"10.1016/j.advmem.2025.100186","url":null,"abstract":"<div><div>Ceramic oxygen separation membranes have advantages over cryogenic distillation and pressure swing adsorption in terms of oxygen production. However, the application of ceramic membranes is restricted by membrane stability issues at high operation temperatures. This study develops ultra-stable oxygen separation membranes through the over-doping of Ni into yttrium-doped zirconia (NYSZ). The Ni doping amount reaches 18.1 mol%, and Ni dissolution substantially increases the electronic conductivity of the yttrium-doped zirconia membranes under both oxidizing and reducing atmospheres, which is as high as 0.96 S cm<sup>−1</sup>. Accordingly, high oxygen permeation rates of up to 1.68 mL min<sup>−1</sup> cm<sup>−2</sup> at 800 °C were achieved, which are comparable with those of conventional perovskite membranes (3.53 mL min<sup>−1</sup> cm<sup>−2</sup>). The ultra-stable NYSZ membranes were confirmed with stable electrochemical reforming of methane for 310 h. Therefore, the robust NYSZ membranes demonstrate great potential in practical applications.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100186"},"PeriodicalIF":9.5,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145529064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01DOI: 10.1016/j.advmem.2025.100180
Li Cao , I-Chun Chen , Cailing Chen , Xiaowei Liu , Kai Qu , Zhen Li , Khalid Hazazi , Zhiping Lai
The salinity gradient between produced water and boiler blowdown water – both significant waste streams in the petroleum industry – represents an emerging, clean, and sustainable energy source. This energy can be directly converted to electricity through reverse electrodialysis. In this study, we developed a series of sulfonated polyether ether ketone (SPEEK)/UiO-66-SO3H mixed matrix membranes specifically tailored for osmotic energy harvesting from these industrial effluents. The incorporation of UiO-66-SO3H nanoparticles into the SPEEK matrix significantly enhanced ion permeance, which can be attributed to the well-defined and appropriately sized pore structure of UiO-66-SO3H. When exploiting the salinity gradient between actual samples of produced water and boiler blowdown water, the membranes containing 20 wt% UiO-66-SO3H achieved a maximum power density of 5.3 W m−2 at an operational temperature of 60 °C. More importantly, these membranes demonstrated high stability during prolonged operational testing, highlighting their potential for sustainable and efficient energy generation from waste streams in the petroleum industry.
采出水和锅炉排污水之间的盐度梯度是石油工业中重要的废物流，代表着一种新兴的、清洁的和可持续的能源。这种能量可以通过反向电渗析直接转化为电能。在这项研究中，我们开发了一系列磺化聚醚醚酮(SPEEK)/UiO-66-SO3H混合基质膜，专门用于从这些工业废水中渗透能量收集。将UiO-66-SO3H纳米颗粒掺入SPEEK基质后，离子渗透性显著增强，这可归因于UiO-66-SO3H孔隙结构清晰且大小合适。当利用实际产出水和锅炉排污水样品之间的盐度梯度时，在60℃的工作温度下，含20wt % uuo -66- so3h的膜的最大功率密度为5.3 W m−2。更重要的是，这些膜在长时间的运行测试中表现出了高稳定性，突出了它们在石油工业废水中可持续高效发电的潜力。
{"title":"Osmotic energy harvesting from produced water and boiler blowdown water by sulfonated Poly(ether ether ketone)-based mixed matrix membranes","authors":"Li Cao , I-Chun Chen , Cailing Chen , Xiaowei Liu , Kai Qu , Zhen Li , Khalid Hazazi , Zhiping Lai","doi":"10.1016/j.advmem.2025.100180","DOIUrl":"10.1016/j.advmem.2025.100180","url":null,"abstract":"<div><div>The salinity gradient between produced water and boiler blowdown water – both significant waste streams in the petroleum industry – represents an emerging, clean, and sustainable energy source. This energy can be directly converted to electricity through reverse electrodialysis. In this study, we developed a series of sulfonated polyether ether ketone (SPEEK)/UiO-66-SO<sub>3</sub>H mixed matrix membranes specifically tailored for osmotic energy harvesting from these industrial effluents. The incorporation of UiO-66-SO<sub>3</sub>H nanoparticles into the SPEEK matrix significantly enhanced ion permeance, which can be attributed to the well-defined and appropriately sized pore structure of UiO-66-SO<sub>3</sub>H. When exploiting the salinity gradient between actual samples of produced water and boiler blowdown water, the membranes containing 20 wt% UiO-66-SO<sub>3</sub>H achieved a maximum power density of 5.3 W m<sup>−2</sup> at an operational temperature of 60 °C. More importantly, these membranes demonstrated high stability during prolonged operational testing, highlighting their potential for sustainable and efficient energy generation from waste streams in the petroleum industry.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100180"},"PeriodicalIF":9.5,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475970","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-31DOI: 10.1016/j.advmem.2025.100183
Chen-Jie Wei , Xun Li , Xing-Yu Chen , Ya-Wei Lin , Dong Yu , He-Lin Zhu , Xue-Li Cao , Bai-Long Xu , Li-Fen Liu
High temperature resistant thin-film composite polyamide (TFC PA) membranes are notable across various applications. However, the pursuit of efficient separation at elevated temperatures was hindered by the thick and unstable active layer. In this work, based on covalent organic frameworks (COFs) decorated with exceptional porosity, remarkably large specific surface areas, and outstanding thermal stability, a TFC PA reverse osmosis (RO) membrane featuring a slimmer selective layer and enhanced thermal stability was achieved through interfacial polymerization mediated by COF nanoparticles as aqueous-phase modifier. Firstly, a novel COFTpDATB nanoparticles with high free volume and rigidity were designed and synthesized based on 3,3′-diamine-Trögers base (DATB) with V-shaped rigid structure and 1,3,5-Triformylphloroglucinol (Tp). The introduction of COFTpDATB nanoparticles retards the penetration of the aqueous phase into the organic phase, facilitating the formation of a thinner and more uniform PA selective layer. The resultant COFTpDATB modified TFC RO membrane exhibited a water permeance of 35.8 L/(m2·h) and high salt rejection rate of 99.6 %. Notably, the hydrogen bond crosslinking density might be increased owing to hydrogen bond formation between carboxyl groups of PA separation layer and a tertiary amine group of COFTpDATB, which further guarantee the high salt rejection under high temperature. The membrane showed a high water permeance of 83.7 L/(m2·h) and rejection rate of 99.1 % even at 70 °C. Overall, enhanced by incorporation of COFTpDATB nanoparticles, TFC PA RO membrane exhibited excellent thermal stability and separation efficiency. The current work is envisaged to supply direction for the high-performance TFC PA RO membrane for high temperature resistance.
耐高温薄膜复合聚酰胺（TFC PA）膜在各种应用中都是值得注意的。然而，在高温下追求有效的分离受到厚厚的和不稳定的活性层的阻碍。在这项工作中，基于共价有机框架（COFs）具有优异的孔隙率，显着的大比表面积和出色的热稳定性，通过COF纳米颗粒作为水相改性剂介导的界面聚合，获得了具有更薄选择层和增强热稳定性的TFC PA反渗透（RO）膜。首先，以具有v型刚性结构的3,3 ' -diamine-Trögers碱（DATB）和1,3,5-三甲酰间苯三酚（Tp）为基材，设计并合成了具有高自由体积和高刚性的新型COFTpDATB纳米颗粒。COFTpDATB纳米颗粒的引入延缓了水相向有机相的渗透，有利于形成更薄、更均匀的PA选择层。所得COFTpDATB改性TFC反渗透膜的渗透率为35.8 L/(m2·h)，盐去除率高达99.6%。值得注意的是，由于PA分离层的羧基与COFTpDATB的叔胺基之间形成氢键，可能会增加氢键交联密度，从而进一步保证了高温下的高阻盐性。在70℃条件下，膜的透水率为83.7 L/(m2·h)，截留率为99.1%。总的来说，COFTpDATB纳米颗粒的加入增强了TFC PA RO膜的热稳定性和分离效率。本研究为高性能TFC PA RO耐高温膜的研究提供了方向。
{"title":"High temperature resistant thin film composite polyamide membrane constructed via 3,3′-diamine-Tröger base COFs for enhancing reverse osmosis separation performances","authors":"Chen-Jie Wei , Xun Li , Xing-Yu Chen , Ya-Wei Lin , Dong Yu , He-Lin Zhu , Xue-Li Cao , Bai-Long Xu , Li-Fen Liu","doi":"10.1016/j.advmem.2025.100183","DOIUrl":"10.1016/j.advmem.2025.100183","url":null,"abstract":"<div><div>High temperature resistant thin-film composite polyamide (TFC PA) membranes are notable across various applications. However, the pursuit of efficient separation at elevated temperatures was hindered by the thick and unstable active layer. In this work, based on covalent organic frameworks (COFs) decorated with exceptional porosity, remarkably large specific surface areas, and outstanding thermal stability, a TFC PA reverse osmosis (RO) membrane featuring a slimmer selective layer and enhanced thermal stability was achieved through interfacial polymerization mediated by COF nanoparticles as aqueous-phase modifier. Firstly, a novel COF<sub>TpDATB</sub> nanoparticles with high free volume and rigidity were designed and synthesized based on 3,3′-diamine-Trögers base (DATB) with V-shaped rigid structure and 1,3,5-Triformylphloroglucinol (Tp). The introduction of COF<sub>TpDATB</sub> nanoparticles retards the penetration of the aqueous phase into the organic phase, facilitating the formation of a thinner and more uniform PA selective layer. The resultant COF<sub>TpDATB</sub> modified TFC RO membrane exhibited a water permeance of 35.8 L/(m<sup>2</sup>·h) and high salt rejection rate of 99.6 %. Notably, the hydrogen bond crosslinking density might be increased owing to hydrogen bond formation between carboxyl groups of PA separation layer and a tertiary amine group of COF<sub>TpDATB</sub>, which further guarantee the high salt rejection under high temperature. The membrane showed a high water permeance of 83.7 L/(m<sup>2</sup>·h) and rejection rate of 99.1 % even at 70 °C. Overall, enhanced by incorporation of COF<sub>TpDATB</sub> nanoparticles, TFC PA RO membrane exhibited excellent thermal stability and separation efficiency. The current work is envisaged to supply direction for the high-performance TFC PA RO membrane for high temperature resistance.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100183"},"PeriodicalIF":9.5,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-30DOI: 10.1016/j.advmem.2025.100174
Jing Wang , Guoke Zhao , Bo Chen , Gongqing Tang , Yiqun Liu , Pei Li
Two series of soluble polyimides based on pyromellitic dianhydride (PMDA) were synthesized and investigated for gas separation applications. The first series was prepared by reacting PMDA with 5(6)-1-(4-aminophenyl)-1,3,3′-trimethylindane (5(6)-DAPI). Two commercially available DAPI mixtures, designated as DAPI-1 and DAPI-2, containing 5-DAPI to 6-DAPI isomer ratios of 36:64 and 44:56, respectively, were employed. The results indicated that the higher structural distortion associated with 6-DAPI in PMDA-DAPI-1 demonstrated greater gas permeability but lower selectivity compared to PMDA-DAPI-2. The second series of polyimides utilized diethyl toluene diamine (DETDA). Particular emphasis was placed on polyimides obtained through the copolymerization of DETDA with either 2,4,6-trimethyl-1,3-diaminobenzene (DAM) or 1,5-diaminonaphthalene (NDA), at a diamino monomer ratio of 3:1. The PMDA-DETDA polyimide exhibited higher gas permeability but lower selectivity compared to copolyimide counterparts. Notably, DETDA-based polyimides exhibited CO2/CH4 separation performances approaching the 1991 Robeson upper bound under mixed gas conditions. Furthermore, two series of polyimides showed high glass transition temperatures (Tg) ranging from 461 °C to 534 °C, suggesting their suitability for high-temperature gas separation applications.
{"title":"Gas separation performance of soluble PMDA-polyimides controlled by diamine isomerism and copolymerization","authors":"Jing Wang , Guoke Zhao , Bo Chen , Gongqing Tang , Yiqun Liu , Pei Li","doi":"10.1016/j.advmem.2025.100174","DOIUrl":"10.1016/j.advmem.2025.100174","url":null,"abstract":"<div><div>Two series of soluble polyimides based on pyromellitic dianhydride (PMDA) were synthesized and investigated for gas separation applications. The first series was prepared by reacting PMDA with 5(6)-1-(4-aminophenyl)-1,3,3′-trimethylindane (5(6)-DAPI). Two commercially available DAPI mixtures, designated as DAPI-1 and DAPI-2, containing 5-DAPI to 6-DAPI isomer ratios of 36:64 and 44:56, respectively, were employed. The results indicated that the higher structural distortion associated with 6-DAPI in PMDA-DAPI-1 demonstrated greater gas permeability but lower selectivity compared to PMDA-DAPI-2. The second series of polyimides utilized diethyl toluene diamine (DETDA). Particular emphasis was placed on polyimides obtained through the copolymerization of DETDA with either 2,4,6-trimethyl-1,3-diaminobenzene (DAM) or 1,5-diaminonaphthalene (NDA), at a diamino monomer ratio of 3:1. The PMDA-DETDA polyimide exhibited higher gas permeability but lower selectivity compared to copolyimide counterparts. Notably, DETDA-based polyimides exhibited CO<sub>2</sub>/CH<sub>4</sub> separation performances approaching the 1991 Robeson upper bound under mixed gas conditions. Furthermore, two series of polyimides showed high glass transition temperatures (Tg) ranging from 461 °C to 534 °C, suggesting their suitability for high-temperature gas separation applications.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100174"},"PeriodicalIF":9.5,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-28DOI: 10.1016/j.advmem.2025.100185
Zichen Li , Yumei Wang , Runhao Li , Yi Liu , Yue Sun
Enantiomers of chiral drugs frequently exhibit distinct pharmacological activities, metabolic pathways, rates of metabolism, and toxicological profiles. Consequently, the large-scale production of single enantiomers holds significant scientific and economic value. Membrane-based chiral separation presents considerable potential advantages, including low operational costs and high productivity, which have driven substantial research interest. In this study, we employed the chiral spirocyclic compound 1,1′-spirobiindane-7,7′-diol (SPINOL) as the aqueous-phase monomer to fabricate chiral polymers of intrinsic microporosity (CPIMs) membranes via interfacial polymerization (IP). The S-CPIMs/PAN composite membrane, synthesized on a polyacrylonitrile (PAN) substrate, demonstrated high enantioselectivity towards ibuprofen (PRF), achieving an enantiomeric excess (ee) of 95.4 %. Mechanistically, this selectivity originates from transition-state energy differentials within transmembrane free-energy landscapes. Importantly, large-area, defect-free chiral membranes were successfully fabricated and engineered into functional membrane modules, which demonstrated exceptional homogeneity and stable performance.
{"title":"Intrinsic chiral microporous polymer membranes by interfacial polymerization for precise enantioseparation","authors":"Zichen Li , Yumei Wang , Runhao Li , Yi Liu , Yue Sun","doi":"10.1016/j.advmem.2025.100185","DOIUrl":"10.1016/j.advmem.2025.100185","url":null,"abstract":"<div><div>Enantiomers of chiral drugs frequently exhibit distinct pharmacological activities, metabolic pathways, rates of metabolism, and toxicological profiles. Consequently, the large-scale production of single enantiomers holds significant scientific and economic value. Membrane-based chiral separation presents considerable potential advantages, including low operational costs and high productivity, which have driven substantial research interest. In this study, we employed the chiral spirocyclic compound 1,1′-spirobiindane-7,7′-diol (SPINOL) as the aqueous-phase monomer to fabricate chiral polymers of intrinsic microporosity (CPIMs) membranes via interfacial polymerization (IP). The S-CPIMs/PAN composite membrane, synthesized on a polyacrylonitrile (PAN) substrate, demonstrated high enantioselectivity towards ibuprofen (PRF), achieving an enantiomeric excess (<em>ee</em>) of 95.4 %. Mechanistically, this selectivity originates from transition-state energy differentials within transmembrane free-energy landscapes. Importantly, large-area, defect-free chiral membranes were successfully fabricated and engineered into functional membrane modules, which demonstrated exceptional homogeneity and stable performance.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100185"},"PeriodicalIF":9.5,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145529065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-28DOI: 10.1016/j.advmem.2025.100184
Zhihao Huang , Chuanlong Li , Yuanyuan Sheng , Liqiu Yang , Haoli Zhou , Wanqin Jin
Pervaporation (PV) is considered one of the most industrially potential phenol wastewater treatment technologies because of its advantages such as high efficiency and without regeneration. PV membrane performance is a key factor that determines its industrial applicability. Here, polymer-filler-based mixed matrix membranes (MMMs) are proposed to enhance the membrane performance for pervaporation of phenol aqueous solutions. First, three hyper-crosslinked polymer (HCP) fillers were synthesized via the Friedel–Crafts reaction between benzyl alcohol (BA) and a penta-heterocyclic compound, such as furan (Fu), and analyzed by different characterizations. All the fillers exhibited desirable properties such as high phenol adsorption capacity and excellent hydrophobicity. Subsequently, different MMMs were fabricated by incorporating the HCP fillers into poly (ether block amide) (PEBA-2533) for the separation of phenol aqueous solutions. The Fu/BA-HCP@PEBA-2533 MMM was selected for further investigation as it afforded the highest separation factor of 72.2 and a flux of 2.07 kg/(m2·h) at 70 °C for the separation of a 1.5 wt% phenol aqueous solution. The diffusion and solubility coefficients were measured. The effects of different operating conditions on the membrane performance and long-term stability were studied, and the results for the pervaporation of phenol aqueous solutions were compared with previously reported data. Investigating the effects of diverse polymer fillers and their compatibility with polymers on the fabrication and performance of MMMs will be a prospective future research direction.
{"title":"Poly (ether block amide) membranes with hyper-crosslinked polymer fillers for enhanced pervaporation of phenol aqueous solutions","authors":"Zhihao Huang , Chuanlong Li , Yuanyuan Sheng , Liqiu Yang , Haoli Zhou , Wanqin Jin","doi":"10.1016/j.advmem.2025.100184","DOIUrl":"10.1016/j.advmem.2025.100184","url":null,"abstract":"<div><div>Pervaporation (PV) is considered one of the most industrially potential phenol wastewater treatment technologies because of its advantages such as high efficiency and without regeneration. PV membrane performance is a key factor that determines its industrial applicability. Here, polymer-filler-based mixed matrix membranes (MMMs) are proposed to enhance the membrane performance for pervaporation of phenol aqueous solutions. First, three hyper-crosslinked polymer (HCP) fillers were synthesized via the Friedel–Crafts reaction between benzyl alcohol (BA) and a penta-heterocyclic compound, such as furan (Fu), and analyzed by different characterizations. All the fillers exhibited desirable properties such as high phenol adsorption capacity and excellent hydrophobicity. Subsequently, different MMMs were fabricated by incorporating the HCP fillers into poly (ether block amide) (PEBA-2533) for the separation of phenol aqueous solutions. The Fu/BA-HCP@PEBA-2533 MMM was selected for further investigation as it afforded the highest separation factor of 72.2 and a flux of 2.07 kg/(m<sup>2</sup>·h) at 70 °C for the separation of a 1.5 wt% phenol aqueous solution. The diffusion and solubility coefficients were measured. The effects of different operating conditions on the membrane performance and long-term stability were studied, and the results for the pervaporation of phenol aqueous solutions were compared with previously reported data. Investigating the effects of diverse polymer fillers and their compatibility with polymers on the fabrication and performance of MMMs will be a prospective future research direction.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100184"},"PeriodicalIF":9.5,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-24DOI: 10.1016/j.advmem.2025.100182
Wei-Long Li , Jiao-Rong Li , Guo-Qiang Li , Xiang Kun Cui , Wen-Long Xue , Ming Hao Li , Zhongfeng Li , Hongliang Dong , Chong-Qing Wan
Metal-Organic Frameworks (MOFs) have been demonstrated to be the perfect candidates of function materials for special specie separation. Although numerous MOFs, nearly 100,000 unique ones, have been explored, only several MOF-based membranes are reported because their lack of processability and grain boundary effects seriously limit their fabrication into thin film. This work discusses a strategy of flux melting, ‘borrowed from inorganic domain’, to prepare a MOF thin film via a simple heat-pressing process by using one meltable MOF and a non-meltable MOF. We observed the flux melting of the non-meltable Zr-MOFs and its meltable derivative modified by the binary ionic liquids, the proportion effect of each part on the melting, processability and film nanofiltration for dye molecules. The melt-quenched glass thin film possesses the network inherited from the pristine MOF via the melt, linker exchange and vitrification mechanism. The interesting pore recovery of MOF upon a solvent stimulation endows the film with pore size control (∼1.2 nm) on the dye molecule separation. A 99.88 % rejection rate and a permeability of 27.7 L/m2·h·bar for Congo red dye solution is observed, which is much better than that of analogous MOF membranes generally obtained through complicate processes.
{"title":"Flux melting of UiO-67 family metal-organic frameworks: the thin film processing and nanofiltration property","authors":"Wei-Long Li , Jiao-Rong Li , Guo-Qiang Li , Xiang Kun Cui , Wen-Long Xue , Ming Hao Li , Zhongfeng Li , Hongliang Dong , Chong-Qing Wan","doi":"10.1016/j.advmem.2025.100182","DOIUrl":"10.1016/j.advmem.2025.100182","url":null,"abstract":"<div><div>Metal-Organic Frameworks (MOFs) have been demonstrated to be the perfect candidates of function materials for special specie separation. Although numerous MOFs, nearly 100,000 unique ones, have been explored, only several MOF-based membranes are reported because their lack of processability and grain boundary effects seriously limit their fabrication into thin film. This work discusses a strategy of flux melting, ‘borrowed from inorganic domain’, to prepare a MOF thin film via a simple heat-pressing process by using one meltable MOF and a non-meltable MOF. We observed the flux melting of the non-meltable Zr-MOFs and its meltable derivative modified by the binary ionic liquids, the proportion effect of each part on the melting, processability and film nanofiltration for dye molecules. The melt-quenched glass thin film possesses the network inherited from the pristine MOF via the melt, linker exchange and vitrification mechanism. The interesting pore recovery of MOF upon a solvent stimulation endows the film with pore size control (∼1.2 nm) on the dye molecule separation. A 99.88 % rejection rate and a permeability of 27.7 L/m<sup>2</sup>·h·bar for Congo red dye solution is observed, which is much better than that of analogous MOF membranes generally obtained through complicate processes.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100182"},"PeriodicalIF":9.5,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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