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}
Pub Date : 2025-10-23DOI: 10.1016/j.advmem.2025.100181
Yuchao Yang , Bengui Zhang , Qian Liu , Zhenfeng Sun , Chao Yang , Tao Li , Songwei Zhang , Jingjun He , Feixiang Zhai , Zhihan Song , Enlei Zhang , Kangjun Wang
Vanadium redox flow batteries (VRFBs) are emerging as large-scale energy storage devices to solve volatility in the utilization of renewable energy. As key components of VRFBs, membranes still suffer from problems such as high cost, low conductivity, or insufficient stability. Pyridine-containing poly (aryl ether)s have the advantages of low monomer cost, simple synthesis process, and easy processing into membranes. In this work, a series of pyridine-containing poly (aryl ether) (PyPEK, PyPES, and PyPEF) based on different backbones (4,4′-difluorobenzophenone, 4,4′-dichlorodiphenyl sulfone, and perfluorobiphenyl) were synthesized. The effects of the backbones on the membrane swelling behavior, basic membrane properties, battery performance, and stability of the membranes were studied. The PyPEF membrane exhibited excellent battery performance (EE = 93.78 % at 80 mAcm−2, EE = 86.24 % at 200 mAcm−2, and EE = 80.25 % at 300 mAcm−2) and excellent cycling stability (3000 cycles) in VRFB, which is highly attractive for application in VRFB.
{"title":"Enhanced stability of pyridine-containing poly(arylene ether) membranes for vanadium redox flow battery: influence of backbone structure","authors":"Yuchao Yang , Bengui Zhang , Qian Liu , Zhenfeng Sun , Chao Yang , Tao Li , Songwei Zhang , Jingjun He , Feixiang Zhai , Zhihan Song , Enlei Zhang , Kangjun Wang","doi":"10.1016/j.advmem.2025.100181","DOIUrl":"10.1016/j.advmem.2025.100181","url":null,"abstract":"<div><div>Vanadium redox flow batteries (VRFBs) are emerging as large-scale energy storage devices to solve volatility in the utilization of renewable energy. As key components of VRFBs, membranes still suffer from problems such as high cost, low conductivity, or insufficient stability. Pyridine-containing poly (aryl ether)s have the advantages of low monomer cost, simple synthesis process, and easy processing into membranes. In this work, a series of pyridine-containing poly (aryl ether) (PyPEK, PyPES, and PyPEF) based on different backbones (4,4′-difluorobenzophenone, 4,4′-dichlorodiphenyl sulfone, and perfluorobiphenyl) were synthesized. The effects of the backbones on the membrane swelling behavior, basic membrane properties, battery performance, and stability of the membranes were studied. The PyPEF membrane exhibited excellent battery performance (EE = 93.78 % at 80 mAcm<sup>−2</sup>, EE = 86.24 % at 200 mAcm<sup>−2</sup>, and EE = 80.25 % at 300 mAcm<sup>−2</sup>) and excellent cycling stability (3000 cycles) in VRFB, which is highly attractive for application in VRFB.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100181"},"PeriodicalIF":9.5,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398635","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 : 2025-10-23DOI: 10.1016/j.advmem.2025.100179
Wenjing Ma , Zixin Lv , Xiaowei Zhou , Junhao Xin , Huifeng Wang , Zhiguang Zhang , Xiuling Chen , Nanwen Li
Membrane-based solid polymer electrolytes (SPEs) have emerged as promising candidates for enhancing the energy density and safety of lithium metal battery (LMBs), owing to their superior Li-salt dissociation capability, excellent lithium metal anode compatibility, and cost-effectiveness. However, conventional SPEs often suffer from limited thermal stability, low ionic conductivity, and inadequate mechanical strength. In this study, we developed a novel polymeric membrane incorporating CF3 and amide functional groups, which was subsequently imbibed with lithium salt and solvents to form a homogeneous ternary electrolyte system of polymer/solvent/lithium-ion solvated membranes (ISMs). The resulting ion solvated membranes exhibit remarkable mechanical properties, high ionic conductivity and high security. The amide groups effectively anchor anions and coordinate with Li+, while the strong electron-withdrawing effect of -CF3 groups facilitates the formation of efficient Li + transport channels. Density functional theory (DFT) calculations confirmed that lithium ions preferentially bind to the amide and -CF3 groups rather than solvent molecules, The binding energy between co-FPA and Li+ was calculated to be −3.40 eV, indicating a strong interaction. ISMs demonstrate outstanding electrochemical performance, achieving an ionic conductivity of 1.845 × 10−4 S cm−1 and a high Li + transference number of 0.66. When assembled into Li/co-FPA-50/LFP cells, the system maintains 93 % capacity retention after 200 cycles at 0.5C (initial capacity: 158.6 mAh g−1). The ISM-based quasi-solid-state lithium batteries exhibit exceptional long-term cycling stability over 1000 cycles. This work presents an innovative approach for designing high-performance ion solvated membranes, addressing critical challenges in the development of safe and stable lithium metal batteries.
膜基固体聚合物电解质(spe)由于其优异的锂盐解离能力、优异的锂金属阳极兼容性和成本效益,已成为提高锂金属电池(lmb)能量密度和安全性的有希望的候选者。然而,传统的spe通常存在热稳定性有限、离子电导率低和机械强度不足的问题。在本研究中,我们开发了一种含有CF3和酰胺官能团的新型聚合物膜,随后将其与锂盐和溶剂一起吸收,形成聚合物/溶剂/锂离子溶剂化膜(ISMs)的均相三元电解质体系。所得离子溶剂化膜具有优异的力学性能、高离子电导率和高安全性。酰胺基团有效地锚定阴离子并与Li+配位,而-CF3基团的强吸电子效应有利于形成高效的Li+输运通道。密度泛函理论(DFT)计算证实,锂离子优先结合酰胺和-CF3基团而不是溶剂分子,co-FPA与Li+之间的结合能为- 3.40 eV,表明相互作用强。ISMs具有优异的电化学性能,离子电导率为1.845 × 10−4 S cm−1,Li +迁移数为0.66。当组装成Li/co-FPA-50/LFP电池时,系统在0.5C下循环200次后保持93%的容量保持(初始容量:158.6 mAh g−1)。基于ism的准固态锂电池表现出超过1000次循环的长期稳定性。这项工作提出了一种设计高性能离子溶剂化膜的创新方法,解决了开发安全稳定的锂金属电池的关键挑战。
{"title":"Fluorinated polyamide-based ion-solvating membranes for long-cycle quasi-solid-state lithium batteries","authors":"Wenjing Ma , Zixin Lv , Xiaowei Zhou , Junhao Xin , Huifeng Wang , Zhiguang Zhang , Xiuling Chen , Nanwen Li","doi":"10.1016/j.advmem.2025.100179","DOIUrl":"10.1016/j.advmem.2025.100179","url":null,"abstract":"<div><div>Membrane-based solid polymer electrolytes (SPEs) have emerged as promising candidates for enhancing the energy density and safety of lithium metal battery (LMBs), owing to their superior Li-salt dissociation capability, excellent lithium metal anode compatibility, and cost-effectiveness. However, conventional SPEs often suffer from limited thermal stability, low ionic conductivity, and inadequate mechanical strength. In this study, we developed a novel polymeric membrane incorporating CF<sub>3</sub> and amide functional groups, which was subsequently imbibed with lithium salt and solvents to form a homogeneous ternary electrolyte system of polymer/solvent/lithium-ion solvated membranes (ISMs). The resulting ion solvated membranes exhibit remarkable mechanical properties, high ionic conductivity and high security. The amide groups effectively anchor anions and coordinate with Li<sup>+</sup>, while the strong electron-withdrawing effect of -CF<sub>3</sub> groups facilitates the formation of efficient Li <sup>+</sup> transport channels. Density functional theory (DFT) calculations confirmed that lithium ions preferentially bind to the amide and -CF<sub>3</sub> groups rather than solvent molecules, The binding energy between co-FPA and Li<sup>+</sup> was calculated to be −3.40 eV, indicating a strong interaction. ISMs demonstrate outstanding electrochemical performance, achieving an ionic conductivity of 1.845 × 10<sup>−4</sup> S cm<sup>−1</sup> and a high Li <sup>+</sup> transference number of 0.66. When assembled into Li/co-FPA-50/LFP cells, the system maintains 93 % capacity retention after 200 cycles at 0.5C (initial capacity: 158.6 mAh g<sup>−1</sup>). The ISM-based quasi-solid-state lithium batteries exhibit exceptional long-term cycling stability over 1000 cycles. This work presents an innovative approach for designing high-performance ion solvated membranes, addressing critical challenges in the development of safe and stable lithium metal batteries.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100179"},"PeriodicalIF":9.5,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475968","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 : 2025-10-22DOI: 10.1016/j.advmem.2025.100178
Renqiang Cao , Feng Duan , Wenyan Ji , Jingya Yin , Yujiao Li , Shaoyuan Shi , Yuping Li , Hongbin Cao
Organic fouling of anion exchange membranes (AEMs) severely limits the large-scale application of electrodialysis (ED) in industrial wastewater resource recovery, primarily due to the compromised engineering feasibility of ex-situ modifications requiring stack disassembly. To address this, we developed an efficient strategy enabling in-situ directional construction of an interfacial polymerization (IP) modified layer within ED stacks, significantly enhancing AEM antifouling performance. This approach leverages direct-current electric field to directionally deposit tannic acid (TA) onto AEM surfaces, followed by injection of trimesoyl chloride (TMC) to initiate polymerization, enabling in-situ constructing of IP-modified layers. Optimized conditions yielded [email protected] g/L-AEM (TMC: 1.0 g/L) with maximized esterification degree and surface charge density (−31.25 mV), exhibiting superior antifouling performance. In sodium dodecyl sulfonate (SDS) fouling tests, [email protected] g/L maintained 24.29 % higher desalination rate than pristine membrane stacks at 120 min and exhibited exceptional operational stability (>1200 min). Mechanistic analysis revealed that the in-situ IP-modified layer synergistically suppresses foulant aggregation in the diffusion boundary layer through enhanced surface negative charge density and stability compared to solely electrodeposited TA. This work provides a scalable approach for in-situ construction of modified layers within ED stacks.
{"title":"Enhanced antifouling performance of anion exchange membrane via in-situ constructed interfacial polymerization modified layer within electrodialysis stack","authors":"Renqiang Cao , Feng Duan , Wenyan Ji , Jingya Yin , Yujiao Li , Shaoyuan Shi , Yuping Li , Hongbin Cao","doi":"10.1016/j.advmem.2025.100178","DOIUrl":"10.1016/j.advmem.2025.100178","url":null,"abstract":"<div><div>Organic fouling of anion exchange membranes (AEMs) severely limits the large-scale application of electrodialysis (ED) in industrial wastewater resource recovery, primarily due to the compromised engineering feasibility of ex-situ modifications requiring stack disassembly. To address this, we developed an efficient strategy enabling in-situ directional construction of an interfacial polymerization (IP) modified layer within ED stacks, significantly enhancing AEM antifouling performance. This approach leverages direct-current electric field to directionally deposit tannic acid (TA) onto AEM surfaces, followed by injection of trimesoyl chloride (TMC) to initiate polymerization, enabling in-situ constructing of IP-modified layers. Optimized conditions yielded [email protected] g/L-AEM (TMC: 1.0 g/L) with maximized esterification degree and surface charge density (−31.25 mV), exhibiting superior antifouling performance. In sodium dodecyl sulfonate (SDS) fouling tests, [email protected] g/L maintained 24.29 % higher desalination rate than pristine membrane stacks at 120 min and exhibited exceptional operational stability (>1200 min). Mechanistic analysis revealed that the in-situ IP-modified layer synergistically suppresses foulant aggregation in the diffusion boundary layer through enhanced surface negative charge density and stability compared to solely electrodeposited TA. This work provides a scalable approach for in-situ construction of modified layers within ED stacks.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100178"},"PeriodicalIF":9.5,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475969","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 : 2025-10-17DOI: 10.1016/j.advmem.2025.100177
Anniza Cornelia Augusty, Linhua Fan, Seungju Kim
Thermally driven membrane separation processes, such as membrane distillation (MD) and pervaporation (PV), are emerging technologies for desalination and water treatment applications. While both processes offer high separation efficiency and water productivity, their practical applications are often hindered by membrane fouling. In particular, the accumulation of organic foulants on membrane surfaces, resulting from specific interactions between the foulants and the membrane, poses a persistent challenge. This review provides a critical comparison of the fouling mechanisms observed in hydrophobic, porous MD membranes versus hydrophilic, non-porous PV membranes. It further examines recent advancements in membrane material development, including novel membrane designs, surface modifications, and patterning strategies aimed at mitigating organic fouling in both systems. Key challenges and future research directions are also discussed, with a focus on the development of advanced membrane materials and innovative pretreatment and cleaning strategies to enhance the viability of thermally driven membrane technologies in real-world applications.
{"title":"Emerging trends in fouling mitigation for membrane distillation and pervaporation: Implications for desalination and wastewater treatment","authors":"Anniza Cornelia Augusty, Linhua Fan, Seungju Kim","doi":"10.1016/j.advmem.2025.100177","DOIUrl":"10.1016/j.advmem.2025.100177","url":null,"abstract":"<div><div>Thermally driven membrane separation processes, such as membrane distillation (MD) and pervaporation (PV), are emerging technologies for desalination and water treatment applications. While both processes offer high separation efficiency and water productivity, their practical applications are often hindered by membrane fouling. In particular, the accumulation of organic foulants on membrane surfaces, resulting from specific interactions between the foulants and the membrane, poses a persistent challenge. This review provides a critical comparison of the fouling mechanisms observed in hydrophobic, porous MD membranes versus hydrophilic, non-porous PV membranes. It further examines recent advancements in membrane material development, including novel membrane designs, surface modifications, and patterning strategies aimed at mitigating organic fouling in both systems. Key challenges and future research directions are also discussed, with a focus on the development of advanced membrane materials and innovative pretreatment and cleaning strategies to enhance the viability of thermally driven membrane technologies in real-world applications.</div></div>","PeriodicalId":100033,"journal":{"name":"Advanced Membranes","volume":"6 ","pages":"Article 100177"},"PeriodicalIF":9.5,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145398634","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}