Pub Date : 2025-12-31DOI: 10.3390/membranes16010012
Pegah Naghshnejad, Debojyoti Das, Jose A Romagnoli, Revati Kumar, Jianhua Chen
Anion exchange membranes (AEMs) play a vital role in the performance of water electrolyzers and fuel cells, yet their discovery and optimization remain challenging due to the complexity of structure-property relationships. In this study, we introduce a machine learning framework that leverages conditional graph neural networks (cGNNs) and descriptor-based models and a hybrid graph neural network (HGARE) to predict and interpret ionic conductivity. The descriptor-based pipeline employs principal component analysis (PCA), ablation, and SHAP analysis to identify factors governing anion conductivity, revealing electronic, topological, and compositional descriptors as key contributors. Beyond prediction, dimensionality reduction and clustering are performed by employing t-SNE and KMeans as well as SOM, which reveal distinct membranes clusters, some of which were enriched with high anion conductivity. Among graph-based approaches, the graph convolutional (GCN) achieved strong predictive performance, while the Hybrid Graph Autoencoder-Regressor Ensemble (HGARE) achieved the highest accuracy. Additionally, atom-level saliency maps from GCN provide spatial explanations for conductive behavior, revealing the importance of polarizable and flexible regions. This work contributes to the accelerated and data-driven design of high-performance AEMs.
{"title":"Uncovering Structure-Conductivity Relationships in Anion Exchange Membranes (AEMs) Using Interpretable Machine Learning.","authors":"Pegah Naghshnejad, Debojyoti Das, Jose A Romagnoli, Revati Kumar, Jianhua Chen","doi":"10.3390/membranes16010012","DOIUrl":"10.3390/membranes16010012","url":null,"abstract":"<p><p>Anion exchange membranes (AEMs) play a vital role in the performance of water electrolyzers and fuel cells, yet their discovery and optimization remain challenging due to the complexity of structure-property relationships. In this study, we introduce a machine learning framework that leverages conditional graph neural networks (cGNNs) and descriptor-based models and a hybrid graph neural network (HGARE) to predict and interpret ionic conductivity. The descriptor-based pipeline employs principal component analysis (PCA), ablation, and SHAP analysis to identify factors governing anion conductivity, revealing electronic, topological, and compositional descriptors as key contributors. Beyond prediction, dimensionality reduction and clustering are performed by employing t-SNE and KMeans as well as SOM, which reveal distinct membranes clusters, some of which were enriched with high anion conductivity. Among graph-based approaches, the graph convolutional (GCN) achieved strong predictive performance, while the Hybrid Graph Autoencoder-Regressor Ensemble (HGARE) achieved the highest accuracy. Additionally, atom-level saliency maps from GCN provide spatial explanations for conductive behavior, revealing the importance of polarizable and flexible regions. This work contributes to the accelerated and data-driven design of high-performance AEMs.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12843994/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.3390/membranes16010013
Jiayi Xun, Lu Wang, Fengwei Jia, Ziwen Han, Haoran Ma, Yiping Feng, Ying Zhao, Wenjuan Zhang, Dan Song, Jun Ma
Nitrogen, a prevalent water pollutant, is a major cause of eutrophication and the formation of black, odorous water bodies, posing significant threats to both ecological security and human health. Effectively controlling nitrogen pollution in wastewater is therefore essential for preserving aquatic ecosystems. The membrane bioreactor (MBR), which integrates the advantages of biological and membrane technologies, has attracted considerable attention for its application potential in wastewater nitrogen removal. This article elucidates the mechanisms and characteristics of nitrogen removal in MBR systems based on the latest research advancements. It provides an in-depth analysis of the key environmental factors affecting nitrogen removal efficiency and comprehensively summarizes enhanced processes centered on MBR technology. Furthermore, the article addresses corresponding strategies for mitigating MBR membrane fouling and offers suggestions and prospects for future research directions.
{"title":"Enhancing Nitrogen Removal in MBRs: From Theoretical Advances to Practical Applications.","authors":"Jiayi Xun, Lu Wang, Fengwei Jia, Ziwen Han, Haoran Ma, Yiping Feng, Ying Zhao, Wenjuan Zhang, Dan Song, Jun Ma","doi":"10.3390/membranes16010013","DOIUrl":"10.3390/membranes16010013","url":null,"abstract":"<p><p>Nitrogen, a prevalent water pollutant, is a major cause of eutrophication and the formation of black, odorous water bodies, posing significant threats to both ecological security and human health. Effectively controlling nitrogen pollution in wastewater is therefore essential for preserving aquatic ecosystems. The membrane bioreactor (MBR), which integrates the advantages of biological and membrane technologies, has attracted considerable attention for its application potential in wastewater nitrogen removal. This article elucidates the mechanisms and characteristics of nitrogen removal in MBR systems based on the latest research advancements. It provides an in-depth analysis of the key environmental factors affecting nitrogen removal efficiency and comprehensively summarizes enhanced processes centered on MBR technology. Furthermore, the article addresses corresponding strategies for mitigating MBR membrane fouling and offers suggestions and prospects for future research directions.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12844031/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.3390/membranes16010014
Noel Devaere, Vladimiros G Papangelakis
Efficient water recycling in the hydrometallurgical industry requires the dewatering of hypersaline Na2SO4 or similar brines via non-evaporative methods. Unfortunately, many non-evaporative methods require the use of specific solutes and are not compatible with complex hydrometallurgical effluents. Forward Osmosis (FO) uses a draw solution to link known non-evaporative water recycling methods with feed solutions that are otherwise incompatible. There is minimal experimental data on the dewatering performance of today's available commercial FO membranes, especially with hypersaline concentrations (>70,000 mg/L total dissolved solids). This study tests the commercially available Aquaporin HFFO2 hollow fibre FO membrane module with hypersaline Na2SO4 or NaCl feed solutions versus a MgCl2 draw solution. It identifies a key requirement to maintain water flux above a certain threshold to prevent a decrease in Na Rejection or an increase in Mg reverse flux. It also defines a minimum osmotic differential that can be used to parameterize water flux, similar to the temperature of approach in heat exchangers, but to determine the extent of water removal in FO. We demonstrate that even under mildly acidic conditions, existing FO membranes can concentrate Na2SO4 to saturation, paving the way for their use in the hydrometallurgical industry.
{"title":"Dewatering Hypersaline Na<sub>2</sub>SO<sub>4</sub> and NaCl via Commercial Forward Osmosis Module.","authors":"Noel Devaere, Vladimiros G Papangelakis","doi":"10.3390/membranes16010014","DOIUrl":"10.3390/membranes16010014","url":null,"abstract":"<p><p>Efficient water recycling in the hydrometallurgical industry requires the dewatering of hypersaline Na<sub>2</sub>SO<sub>4</sub> or similar brines via non-evaporative methods. Unfortunately, many non-evaporative methods require the use of specific solutes and are not compatible with complex hydrometallurgical effluents. Forward Osmosis (FO) uses a draw solution to link known non-evaporative water recycling methods with feed solutions that are otherwise incompatible. There is minimal experimental data on the dewatering performance of today's available commercial FO membranes, especially with hypersaline concentrations (>70,000 mg/L total dissolved solids). This study tests the commercially available Aquaporin HFFO2 hollow fibre FO membrane module with hypersaline Na<sub>2</sub>SO<sub>4</sub> or NaCl feed solutions versus a MgCl<sub>2</sub> draw solution. It identifies a key requirement to maintain water flux above a certain threshold to prevent a decrease in Na Rejection or an increase in Mg reverse flux. It also defines a minimum osmotic differential that can be used to parameterize water flux, similar to the temperature of approach in heat exchangers, but to determine the extent of water removal in FO. We demonstrate that even under mildly acidic conditions, existing FO membranes can concentrate Na<sub>2</sub>SO<sub>4</sub> to saturation, paving the way for their use in the hydrometallurgical industry.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12844510/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.3390/membranes16010017
Chiara Goisis, Davide Porrelli, Gianluca Turco, Barbara Medagli, Giovanni Papa, Martin Iurilli
Chronic and complex wounds require biomaterials that are both cytocompatible and antimicrobial. Herein, electrospun polycaprolactone (PCL) nanofiber membranes were coated with Type I collagen and functionalized with silver nanoparticles (AgNPs). The main objective was to assess fibroblast adhesion, proliferation, and cytotoxicity. Membrane morphology and surface characteristics were analyzed in a previous work by SEM, AFM, and wettability measurements, confirming the transformation from hydrophobic PCL to fully wettable collagen-coated surfaces. In this study, Murine 3T3 fibroblasts were cultured on PCL, PCL-Collagen, PCL-Collagen-Citrate, and PCL-Collagen-AgNPs membranes. Cellular activity was quantified using Alamar Blue assays at 24, 48, and 72 h, while cytotoxicity was determined by LDH release. Cellular viability and adhesion were studied using confocal microscopy. All membrane types supported fibroblast growth, with collagen-coated samples exhibiting the highest metabolic activity. AgNPs-functionalized membranes sustained overall cell viability above 90%, with cytotoxicity values of approximately 10% at 24 h and 20% at 48 h. Antimicrobial evaluations demonstrated complete inhibition of Pseudomonas aeruginosa and vancomycin-resistant Enterococcus, and partial inhibition of Staphylococcus aureus. These results indicate that collagen-coated, AgNPs-functionalized electrospun PCL membranes exhibit both high cytocompatibility and significant antimicrobial activity, supporting their potential as advanced wound-dressing materials.
{"title":"Cell Adhesion and Cytotoxicity Assessment of Collagen-Coated Electrospun PCL Membranes Functionalized with Silver Nanoparticles.","authors":"Chiara Goisis, Davide Porrelli, Gianluca Turco, Barbara Medagli, Giovanni Papa, Martin Iurilli","doi":"10.3390/membranes16010017","DOIUrl":"10.3390/membranes16010017","url":null,"abstract":"<p><p>Chronic and complex wounds require biomaterials that are both cytocompatible and antimicrobial. Herein, electrospun polycaprolactone (PCL) nanofiber membranes were coated with Type I collagen and functionalized with silver nanoparticles (AgNPs). The main objective was to assess fibroblast adhesion, proliferation, and cytotoxicity. Membrane morphology and surface characteristics were analyzed in a previous work by SEM, AFM, and wettability measurements, confirming the transformation from hydrophobic PCL to fully wettable collagen-coated surfaces. In this study, Murine 3T3 fibroblasts were cultured on PCL, PCL-Collagen, PCL-Collagen-Citrate, and PCL-Collagen-AgNPs membranes. Cellular activity was quantified using Alamar Blue assays at 24, 48, and 72 h, while cytotoxicity was determined by LDH release. Cellular viability and adhesion were studied using confocal microscopy. All membrane types supported fibroblast growth, with collagen-coated samples exhibiting the highest metabolic activity. AgNPs-functionalized membranes sustained overall cell viability above 90%, with cytotoxicity values of approximately 10% at 24 h and 20% at 48 h. Antimicrobial evaluations demonstrated complete inhibition of <i>Pseudomonas aeruginosa</i> and <i>vancomycin-resistant Enterococcus</i>, and partial inhibition of <i>Staphylococcus aureus</i>. These results indicate that collagen-coated, AgNPs-functionalized electrospun PCL membranes exhibit both high cytocompatibility and significant antimicrobial activity, supporting their potential as advanced wound-dressing materials.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12844388/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.3390/membranes16010011
Virjinia Doltchinkova, Victoria Vitkova, Meglena Kitanova, Milena Shkodrova, Siya Lozanova, Avgust Ivanov, Chavdar Roumenin
Many biomedical applications require a detailed understanding of the action of antimicrobial peptides on biological membranes. The cationic hemolytic peptide melittin, a major component of European honey bee (Apis mellifera) venom, is considered a model for elucidating lipid-protein interactions that are important for the function of biological systems. Here, we address the surface properties of human erythrocytes and rat liver mitochondrial membranes under in vitro melittin treatment. These membranes are negatively charged at neutral pH and represent primary targets of melittin's effects in the onset of inflammatory diseases. The correlation between the functional activity of membrane systems and their surface electrical charge was assessed using microelectrophoresis, hemolysis assays, membrane transport measurements, lipid peroxidation analysis, and fluorescence microscopy. A mechanistic hypothesis for the divergent effects of sub-lytic, pre-pore doses of melittin on erythrocytes and mitochondria is discussed. At low concentrations, melittin interacts electrostatically with erythrocyte membranes, resulting in altered proton transport through the Band 3 protein. Melittin also induces changes in erythrocyte morphology and malondialdehyde content, as well as aggregation of mitochondrial vesicles. The electrokinetic mechanism of melittin action, associated with membrane stability, provides a novel perspective on its potential relevance to biomedical applications.
{"title":"On the Effect of Melittin on Surface Properties of Erythrocyte and Mitochondrial Membranes.","authors":"Virjinia Doltchinkova, Victoria Vitkova, Meglena Kitanova, Milena Shkodrova, Siya Lozanova, Avgust Ivanov, Chavdar Roumenin","doi":"10.3390/membranes16010011","DOIUrl":"10.3390/membranes16010011","url":null,"abstract":"<p><p>Many biomedical applications require a detailed understanding of the action of antimicrobial peptides on biological membranes. The cationic hemolytic peptide melittin, a major component of European honey bee (<i>Apis mellifera</i>) venom, is considered a model for elucidating lipid-protein interactions that are important for the function of biological systems. Here, we address the surface properties of human erythrocytes and rat liver mitochondrial membranes under in vitro melittin treatment. These membranes are negatively charged at neutral pH and represent primary targets of melittin's effects in the onset of inflammatory diseases. The correlation between the functional activity of membrane systems and their surface electrical charge was assessed using microelectrophoresis, hemolysis assays, membrane transport measurements, lipid peroxidation analysis, and fluorescence microscopy. A mechanistic hypothesis for the divergent effects of sub-lytic, pre-pore doses of melittin on erythrocytes and mitochondria is discussed. At low concentrations, melittin interacts electrostatically with erythrocyte membranes, resulting in altered proton transport through the Band 3 protein. Melittin also induces changes in erythrocyte morphology and malondialdehyde content, as well as aggregation of mitochondrial vesicles. The electrokinetic mechanism of melittin action, associated with membrane stability, provides a novel perspective on its potential relevance to biomedical applications.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12843780/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ammonia (NH3) recovery from animal manure offers both environmental and economic benefits by reducing nitrogen emissions and producing valuable fertilisers. Hollow fibre membrane contactors (HFMCs) are a promising technology for this purpose, yet their performance is strongly influenced by the complex composition of manure. In this study, the effects of solids concentration and organic foulants concentration on the mass transfer coefficients governing NH3 recovery were systematically investigated. Total suspended solids (TSS) were reduced through graded filtration, and protein concentrations in the ammonium solutions were quantified to assess their role in limiting mass transfer. Results showed that TSS concentration primarily affected the shell-side film resistance. After extensive filtration, residual proteins attached to the membrane surface induced partial wetting, thereby reducing the effective membrane mass transfer coefficient. Using a penalty function approach, it was possible to separately describe TSS- and protein-related resistances, enabling improved prediction of effective model coefficients under real world conditions. These findings highlight the dual importance of solid-liquid separation and protein management in optimising HFMC operation for NH3 recovery and provide a framework for up-scaling the technology in agricultural nutrient management systems.
{"title":"Ammonia Recovery from Animal Manure via Hollow Fibre Membrane Contactors: Impact of Filtration Pre-Treatment and Organic Foulants on Mass Transfer and Performance.","authors":"Niloufar Azizi, Shaun Connolly, Dominika Krol, Eoin Syron","doi":"10.3390/membranes16010015","DOIUrl":"10.3390/membranes16010015","url":null,"abstract":"<p><p>Ammonia (NH<sub>3</sub>) recovery from animal manure offers both environmental and economic benefits by reducing nitrogen emissions and producing valuable fertilisers. Hollow fibre membrane contactors (HFMCs) are a promising technology for this purpose, yet their performance is strongly influenced by the complex composition of manure. In this study, the effects of solids concentration and organic foulants concentration on the mass transfer coefficients governing NH<sub>3</sub> recovery were systematically investigated. Total suspended solids (TSS) were reduced through graded filtration, and protein concentrations in the ammonium solutions were quantified to assess their role in limiting mass transfer. Results showed that TSS concentration primarily affected the shell-side film resistance. After extensive filtration, residual proteins attached to the membrane surface induced partial wetting, thereby reducing the effective membrane mass transfer coefficient. Using a penalty function approach, it was possible to separately describe TSS- and protein-related resistances, enabling improved prediction of effective model coefficients under real world conditions. These findings highlight the dual importance of solid-liquid separation and protein management in optimising HFMC operation for NH<sub>3</sub> recovery and provide a framework for up-scaling the technology in agricultural nutrient management systems.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12843982/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-30DOI: 10.3390/membranes16010010
Veli Batmaz, Necati Kayaalp
In a standard diffuser system in a membrane bioreactor (MBR), uneven air distribution scouring the membrane surface causes transmembrane pressure to reach its ultimate value earlier, which requires membrane cleaning more frequently. In this study, a Venturi-integrated innovative diffuser design is proposed to improve membrane bioreactor (MBR) technology. The proposed design aims to increase filtration efficiency by creating a homogeneous scouring effect on the membrane surface. To compare the performance of the proposed diffuser configuration (V-MBR) with that of a conventional diffuser (S-MBR), computational fluid dynamics models were established for each of the two configurations. The results showed that the V-MBR model produced about 50% higher average shear stress on the membrane surfaces. Statistical analysis also showed that the V-MBR model generally produced low variance and non-zero shear stress values. Along with shear stress distribution, other parameters such as volume fraction, velocity, turbulent kinetic energy, and turbulent eddy distribution were evaluated to compare the performance of two diffuser system configurations. These parameters also supported the superior performance of the new V-MBR model over the conventional S-MBR. It is concluded that homogeneous shear stress distribution on the membrane surface is an important parameter that increases filtration efficiency by preventing the formation of dead zones.
{"title":"Computational Fluid Dynamics Analysis of a Venturi-Integrated Diffuser Design for Membrane Bioreactors.","authors":"Veli Batmaz, Necati Kayaalp","doi":"10.3390/membranes16010010","DOIUrl":"10.3390/membranes16010010","url":null,"abstract":"<p><p>In a standard diffuser system in a membrane bioreactor (MBR), uneven air distribution scouring the membrane surface causes transmembrane pressure to reach its ultimate value earlier, which requires membrane cleaning more frequently. In this study, a Venturi-integrated innovative diffuser design is proposed to improve membrane bioreactor (MBR) technology. The proposed design aims to increase filtration efficiency by creating a homogeneous scouring effect on the membrane surface. To compare the performance of the proposed diffuser configuration (V-MBR) with that of a conventional diffuser (S-MBR), computational fluid dynamics models were established for each of the two configurations. The results showed that the V-MBR model produced about 50% higher average shear stress on the membrane surfaces. Statistical analysis also showed that the V-MBR model generally produced low variance and non-zero shear stress values. Along with shear stress distribution, other parameters such as volume fraction, velocity, turbulent kinetic energy, and turbulent eddy distribution were evaluated to compare the performance of two diffuser system configurations. These parameters also supported the superior performance of the new V-MBR model over the conventional S-MBR. It is concluded that homogeneous shear stress distribution on the membrane surface is an important parameter that increases filtration efficiency by preventing the formation of dead zones.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12844084/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-30DOI: 10.3390/membranes16010008
Ji-Hyeon Lee, Moon-Sung Kang
In bipolar membrane electrodialysis (BPED), proton transport through the anion-exchange membrane (AEM) is a major factor that reduces overall process efficiency. In this study, we propose a composite AEM incorporating a proton-blocking layer that combines strongly basic and weakly basic functional groups on top of a strongly basic AEM, providing proton-blocking capability while minimizing degradation of membrane conductivity. The proton-blocking layer is prepared by reacting brominated poly(phenylene oxide) (BPPO) with diamines having different alkyl chain lengths, namely N,N,N',N'-tetramethyl-1,6-hexanediamine (TMHDA), N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), and N,N,N',N'-tetramethylethylenediamine (TMEDA). When TMHDA, which has the longest alkyl chain, is introduced into PPO, the resulting membrane exhibits high conductivity but low proton-blocking performance. In contrast, when TMEDA, which has the shortest alkyl chain, is introduced, the membrane shows low conductivity and high proton-blocking performance. Therefore, the balance between membrane conductivity and proton-blocking performance can be optimized by adjusting the molar ratio of the two diamines. The composite AEM prepared with the optimal composition simultaneously demonstrates superior conductivity and proton-blocking performance compared to the commercial proton-blocking membrane (ACM, Astom Corp., Tokyo, Japan). Furthermore, the application of this membrane has been shown to effectively improve both the energy efficiency and current efficiency of the BPED process for lithium hydroxide recovery.
在双极膜电渗析(BPED)中,质子通过阴离子交换膜(AEM)的传输是降低整个过程效率的主要因素。在这项研究中,我们提出了一种包含质子阻断层的复合AEM,该层将强碱性和弱碱性官能团结合在强碱性AEM上,提供质子阻断能力,同时最大限度地减少膜电导率的退化。通过溴化聚苯乙烯氧化物(BPPO)与不同烷基链长度的二胺即N,N,N‘,N’-四甲基-1,6-己二胺(TMHDA)、N,N,N‘,N’-四甲基-1,3-丙二胺(TMPDA)和N,N,N‘,N’-四甲基乙二胺(TMEDA)反应制备质子阻断层。将具有最长烷基链的TMHDA引入PPO中,得到的膜具有高导电性但低质子阻断性能。相反,当引入烷基链最短的TMEDA时,膜表现出低电导率和高质子阻断性能。因此,可以通过调节两种二胺的摩尔比来优化膜电导率和质子阻断性能之间的平衡。与商业质子阻断膜(ACM, Astom Corp., Tokyo, Japan)相比,采用最佳成分制备的复合AEM同时具有优越的导电性和质子阻断性能。此外,该膜的应用有效地提高了BPED工艺回收氢氧化锂的能量效率和电流效率。
{"title":"Proton-Blocking Anion-Exchange Membranes for Efficient Lithium Hydroxide Recovery by Bipolar Membrane Electrodialysis.","authors":"Ji-Hyeon Lee, Moon-Sung Kang","doi":"10.3390/membranes16010008","DOIUrl":"10.3390/membranes16010008","url":null,"abstract":"<p><p>In bipolar membrane electrodialysis (BPED), proton transport through the anion-exchange membrane (AEM) is a major factor that reduces overall process efficiency. In this study, we propose a composite AEM incorporating a proton-blocking layer that combines strongly basic and weakly basic functional groups on top of a strongly basic AEM, providing proton-blocking capability while minimizing degradation of membrane conductivity. The proton-blocking layer is prepared by reacting brominated poly(phenylene oxide) (BPPO) with diamines having different alkyl chain lengths, namely <i>N</i>,<i>N</i>,<i>N'</i>,<i>N'</i>-tetramethyl-1,6-hexanediamine (TMHDA), <i>N</i>,<i>N</i>,<i>N'</i>,<i>N'</i>-tetramethyl-1,3-propanediamine (TMPDA), and <i>N</i>,<i>N</i>,<i>N'</i>,<i>N'</i>-tetramethylethylenediamine (TMEDA). When TMHDA, which has the longest alkyl chain, is introduced into PPO, the resulting membrane exhibits high conductivity but low proton-blocking performance. In contrast, when TMEDA, which has the shortest alkyl chain, is introduced, the membrane shows low conductivity and high proton-blocking performance. Therefore, the balance between membrane conductivity and proton-blocking performance can be optimized by adjusting the molar ratio of the two diamines. The composite AEM prepared with the optimal composition simultaneously demonstrates superior conductivity and proton-blocking performance compared to the commercial proton-blocking membrane (ACM, Astom Corp., Tokyo, Japan). Furthermore, the application of this membrane has been shown to effectively improve both the energy efficiency and current efficiency of the BPED process for lithium hydroxide recovery.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12843717/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-30DOI: 10.3390/membranes16010009
Chaoyue Yang, Li Zhou, Qian Zhang, Ya Huang, Peixiao Zhang, Jingwen Xue, Qing Li, Weijie Sun, Jiayou Liao
Tröger's base (TB) polymers have received increasing attention as a novel class of polymers with intrinsic microporosity, particularly for applications in gas separation. In this study, TB was quaternized with hydrophobic long chains to create a microphase-separated structure to enhance gas separation performance. On one hand, the tertiary amine structure of TB enabled facile grafting modification through the Menshutkin reaction. On the other hand, microphase-separated channels were created in the quaternized Tröger's base (QTB) membrane due to the polarity differences between the hydrophilicity of the quaternary ammonium groups and hydrophobicity of iodoalkanes, providing channels for gas transport within the membrane and thereby improving permeability selectivity. The successful synthesis of QTB membranes was confirmed by FTIR and 1H NMR spectroscopy, while AFM and SAXS analyses validated the microphase-separated morphology. To investigate the impact of microphase separation on oxygen permeability and selectivity, different iodoalkanes and various concentrations of iodobutane were grafted onto the TB backbone. Among the prepared membranes, QTB-C4-70% membrane exhibited the highest in O2 permeability. Gas separation performance under different O2 pressures and temperatures revealed that O2 permeability decreased slightly with increasing pressure, indicating good pressure stability of the membrane. With increasing temperature, the permeability increased while the selectivity decreased. These findings demonstrated that microphase-separated QTB membranes offer a viable strategy for creating effective materials for gas separation.
Tröger的碱(TB)聚合物作为一类具有固有微孔隙度的新型聚合物,特别是在气体分离中的应用,越来越受到人们的关注。在本研究中,将TB与疏水长链进行季铵化,形成微相分离结构,以提高气体分离性能。一方面,叔胺结构使得TB可以通过Menshutkin反应进行简单的接枝修饰。另一方面,由于季铵盐基团的亲水性和碘烷烃的疏水性之间的极性差异,在季铵化Tröger’s base (QTB)膜上形成了微相分离通道,为膜内气体输送提供了通道,从而提高了渗透选择性。FTIR和1H NMR分析证实了QTB膜的成功合成,AFM和SAXS分析证实了微相分离的形貌。为了研究微相分离对氧透性和选择性的影响,将不同的碘烷烃和不同浓度的碘丁烷接枝到结核骨架上。在制备的膜中,QTB-C4-70%膜的透氧性最高。不同O2压力和温度下的气体分离性能表明,随着压力的增加,膜的O2渗透率略有下降,表明膜具有良好的压力稳定性。随着温度的升高,渗透率增加,选择性降低。这些发现表明,微相分离的QTB膜为创建有效的气体分离材料提供了一种可行的策略。
{"title":"Fabrication of Microphase-Separated Tröger's Base Polymer Membranes for Oxygen Enrichment.","authors":"Chaoyue Yang, Li Zhou, Qian Zhang, Ya Huang, Peixiao Zhang, Jingwen Xue, Qing Li, Weijie Sun, Jiayou Liao","doi":"10.3390/membranes16010009","DOIUrl":"10.3390/membranes16010009","url":null,"abstract":"<p><p>Tröger's base (TB) polymers have received increasing attention as a novel class of polymers with intrinsic microporosity, particularly for applications in gas separation. In this study, TB was quaternized with hydrophobic long chains to create a microphase-separated structure to enhance gas separation performance. On one hand, the tertiary amine structure of TB enabled facile grafting modification through the Menshutkin reaction. On the other hand, microphase-separated channels were created in the quaternized Tröger's base (QTB) membrane due to the polarity differences between the hydrophilicity of the quaternary ammonium groups and hydrophobicity of iodoalkanes, providing channels for gas transport within the membrane and thereby improving permeability selectivity. The successful synthesis of QTB membranes was confirmed by FTIR and <sup>1</sup>H NMR spectroscopy, while AFM and SAXS analyses validated the microphase-separated morphology. To investigate the impact of microphase separation on oxygen permeability and selectivity, different iodoalkanes and various concentrations of iodobutane were grafted onto the TB backbone. Among the prepared membranes, QTB-C<sub>4</sub>-70% membrane exhibited the highest in O<sub>2</sub> permeability. Gas separation performance under different O<sub>2</sub> pressures and temperatures revealed that O<sub>2</sub> permeability decreased slightly with increasing pressure, indicating good pressure stability of the membrane. With increasing temperature, the permeability increased while the selectivity decreased. These findings demonstrated that microphase-separated QTB membranes offer a viable strategy for creating effective materials for gas separation.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12844488/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052954","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-26DOI: 10.3390/membranes16010007
Volker Bächle, Marco Gleiß, Hermann Nirschl
The filtration of microalgae generates fouling through algal matter and exopolymer particles with consequences for the flow rate. Therefore, regeneration that is as complete and continuous as possible is necessary. For this purpose, a commercial membrane with a pore size of 0.8 µm is contaminated with the microalgae mixture Haematoccocus Pluvialis and Tetradesmus obliquus, and then regenerated with mechanical (backwashing), chemical (HCl, NaOH, NaClO, P3-Ultrasil) and biological (dishwashing and laundry detergents) cleaning methods. The filtration time of the individual experiments is compared with a new membrane, and the increase is determined. Backwashing cleans the pores, but the biofilm sticks to the membrane surface and blocks the pores shortly after a new cycle. It was shown that the biofilm can only be removed chemically through oxidative effects or anionic surfactants. Hydrolysis does not remove the biofilm, and it can actually make the blockage worse. Bigger cellular residues can only be removed with enzymes. This improves cleaning performance by 61% compared to commercial cleaning agents for membranes and 42% compared to backwashing.
{"title":"Characterization of the Regenerative Capacity of Membranes in the Presence of Fouling by Microalgae Using Detergents.","authors":"Volker Bächle, Marco Gleiß, Hermann Nirschl","doi":"10.3390/membranes16010007","DOIUrl":"10.3390/membranes16010007","url":null,"abstract":"<p><p>The filtration of microalgae generates fouling through algal matter and exopolymer particles with consequences for the flow rate. Therefore, regeneration that is as complete and continuous as possible is necessary. For this purpose, a commercial membrane with a pore size of 0.8 µm is contaminated with the microalgae mixture Haematoccocus Pluvialis and Tetradesmus obliquus, and then regenerated with mechanical (backwashing), chemical (HCl, NaOH, NaClO, P3-Ultrasil) and biological (dishwashing and laundry detergents) cleaning methods. The filtration time of the individual experiments is compared with a new membrane, and the increase is determined. Backwashing cleans the pores, but the biofilm sticks to the membrane surface and blocks the pores shortly after a new cycle. It was shown that the biofilm can only be removed chemically through oxidative effects or anionic surfactants. Hydrolysis does not remove the biofilm, and it can actually make the blockage worse. Bigger cellular residues can only be removed with enzymes. This improves cleaning performance by 61% compared to commercial cleaning agents for membranes and 42% compared to backwashing.</p>","PeriodicalId":18410,"journal":{"name":"Membranes","volume":"16 1","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12844485/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146052934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}