Journal of Membrane Science最新文献_第6页

Fast roll-to-roll fabrication of ultrathin silicon oxide/PDMS membrane on PTFE substrate via interfacial plasma crosslinking

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-04-02 DOI: 10.1016/j.memsci.2025.124058

Edhuan Ismail , Takako Tsubata , Fatin B. Fauzi , Mizuki Inoue , László Szabó , Kazuya Nonomura , Toru Morita , Izumi Ichinose

Organic solvent nanofiltration (OSN) membranes offer a promising alternative to the conventional separation technology. A plasma-enhanced chemical vapor deposition (PECVD) of hexamethyldisiloxane (HMDSO) was used to introduce ultrathin silicon oxide layer onto the surface of crosslinked polydimethylsiloxane (PDMS) layer. Based on FTIR analysis and XPS depth profiling, the membrane had a 20 nm silicon oxide layer formed on a rubber-like PDMS layer. The membrane showed very hydrophobic characteristics that remained stable for more than two months. A large area silicon oxide/PDMS membrane of 600 cm² could be prepared by the plasma exposure of a few seconds using flexible, non-woven PTFE substrate. The membrane was resistant to organic solvents such as alkanes, alcohols, and aromatic solvents, and did not show pressure-induced compaction at least up to 3 bar feed pressure. The permeance properties of non-polar solvents obey the Hagen-Poiseuille equation for pressure and viscosity. A membrane with a thickness of 180 nm showed a hexane permeance of 34 L m⁻² h⁻¹ bar⁻¹ at a pressure of 0.5 bar and a molecular weight cut-off (MWCO) of 700 Da. The plasma-assisted interfacial polymerization process introduced here provides a fast, continuous way to fabricate advanced OSN membranes, facilitating the widespread implementation of OSN-based separation technologies in various chemical sectors.

{"title":"Fast roll-to-roll fabrication of ultrathin silicon oxide/PDMS membrane on PTFE substrate via interfacial plasma crosslinking","authors":"Edhuan Ismail , Takako Tsubata , Fatin B. Fauzi , Mizuki Inoue , László Szabó , Kazuya Nonomura , Toru Morita , Izumi Ichinose","doi":"10.1016/j.memsci.2025.124058","DOIUrl":"10.1016/j.memsci.2025.124058","url":null,"abstract":"<div><div>Organic solvent nanofiltration (OSN) membranes offer a promising alternative to the conventional separation technology. A plasma-enhanced chemical vapor deposition (PECVD) of hexamethyldisiloxane (HMDSO) was used to introduce ultrathin silicon oxide layer onto the surface of crosslinked polydimethylsiloxane (PDMS) layer. Based on FTIR analysis and XPS depth profiling, the membrane had a 20 nm silicon oxide layer formed on a rubber-like PDMS layer. The membrane showed very hydrophobic characteristics that remained stable for more than two months. A large area silicon oxide/PDMS membrane of 600 cm<sup>2</sup> could be prepared by the plasma exposure of a few seconds using flexible, non-woven PTFE substrate. The membrane was resistant to organic solvents such as alkanes, alcohols, and aromatic solvents, and did not show pressure-induced compaction at least up to 3 bar feed pressure. The permeance properties of non-polar solvents obey the Hagen-Poiseuille equation for pressure and viscosity. A membrane with a thickness of 180 nm showed a hexane permeance of 34 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> at a pressure of 0.5 bar and a molecular weight cut-off (MWCO) of 700 Da. The plasma-assisted interfacial polymerization process introduced here provides a fast, continuous way to fabricate advanced OSN membranes, facilitating the widespread implementation of OSN-based separation technologies in various chemical sectors.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124058"},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143815366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic insights into enhancing water transport and antifouling performance under high concentration polarization in polyamide membranes

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-04-02 DOI: 10.1016/j.memsci.2025.124060

Jinlong He , Jishan Wu , Yaxuan Yang , Hong Zhang , Xiaobao Tian , Quanyi Wang , Yongjie Liu , Qingyuan Wang , Jingxi Sun

Reverse osmosis (RO)-based polyamide (PA) membranes encounter significant challenges in maintaining water transport efficiency and antifouling capability under high-salinity levels. Although self-assembled monolayer hydrophilic coatings based on polyethylene glycol (PEG) and its derivatives enhance performance at low salinity, their effectiveness diminishes in high-salinity environments. In this study, we employ molecular dynamics simulations to explore a novel modification strategy that integrates poly (ethylene glycol) diacrylate (PEGDA) as a hydrophilic polymer matrix with N,N′-methylenebis (acrylamide) (MBAA) as the mechanical bridge. This approach forms a robust PEGDA-MBAA nanoporous network on PA membranes, which, in comparison to conventional PEG coatings, better preserves hydration, maintains structural integrity, and exhibits enhanced resistance to humic acid fouling across varying salinity levels. These molecular-level insights into salinity-dependent water transport and fouling mechanisms offer a promising pathway for the design of next-generation, high-salinity, low-energy PA membranes for water treatment applications.

{"title":"Mechanistic insights into enhancing water transport and antifouling performance under high concentration polarization in polyamide membranes","authors":"Jinlong He , Jishan Wu , Yaxuan Yang , Hong Zhang , Xiaobao Tian , Quanyi Wang , Yongjie Liu , Qingyuan Wang , Jingxi Sun","doi":"10.1016/j.memsci.2025.124060","DOIUrl":"10.1016/j.memsci.2025.124060","url":null,"abstract":"<div><div>Reverse osmosis (RO)-based polyamide (PA) membranes encounter significant challenges in maintaining water transport efficiency and antifouling capability under high-salinity levels. Although self-assembled monolayer hydrophilic coatings based on polyethylene glycol (PEG) and its derivatives enhance performance at low salinity, their effectiveness diminishes in high-salinity environments. In this study, we employ molecular dynamics simulations to explore a novel modification strategy that integrates poly (ethylene glycol) diacrylate (PEGDA) as a hydrophilic polymer matrix with <em>N</em>,N′-methylenebis (acrylamide) (MBAA) as the mechanical bridge. This approach forms a robust PEGDA-MBAA nanoporous network on PA membranes, which, in comparison to conventional PEG coatings, better preserves hydration, maintains structural integrity, and exhibits enhanced resistance to humic acid fouling across varying salinity levels. These molecular-level insights into salinity-dependent water transport and fouling mechanisms offer a promising pathway for the design of next-generation, high-salinity, low-energy PA membranes for water treatment applications.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124060"},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Design of high antifouling pH-responsive membrane for anionic dye filtration under alkaline conditions 设计用于碱性条件下阴离子染料过滤的高防污 pH 响应膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-04-02 DOI: 10.1016/j.memsci.2025.124055

Kuo-Liang Chuang , Yi-Chen Lin , Fu-Hsien Hsu , Cheng-Kun Lin , Maria-Chiara Ferrari , Hui-Hsin Tseng

In this work, a novel high-antifouling poly(vinylidene fluoride) (PVDF) composite membrane was synthesized via free radical polymerization by incorporating a pH-responsive poly(N-acryloyl-l-alanine) (poly(Ala-OH)) as a functional skin layer and 2-hydroxyethyl acrylate-terminated poly(styrene-alt-maleic anhydride) (SMA-HEA) as an amphiphilic linker for effective integration onto the PVDF substrate. FT-IR and XRD analyses confirmed the successful grafting of poly(Ala-OH) through the CC bond of the linker, leading to a significant enhancement in membrane hydrophilicity. As a result, the modified membranes exhibited a hydrophilic surface. The pH-responsive behavior of the membrane was evident under alkaline conditions (pH = 11), where deprotonation of carboxylic acid groups induced a stronger negative surface charge, causing molecular chain expansion due to electrostatic repulsion. This structural adjustment further improved membrane hydrophilicity and anionic dye rejection. Consequently, the poly(Ala–OH)–modified PVDF membrane demonstrated higher and more stable flux during cyclic filtration tests under alkaline conditions. The results highlight the critical role of the poly(Ala-OH) layer's carboxylic acid groups and membrane charge variations in significantly enhancing overall hydrophilicity and antifouling performance, making it a promising solution for anionic dye filtration.

{"title":"Design of high antifouling pH-responsive membrane for anionic dye filtration under alkaline conditions","authors":"Kuo-Liang Chuang , Yi-Chen Lin , Fu-Hsien Hsu , Cheng-Kun Lin , Maria-Chiara Ferrari , Hui-Hsin Tseng","doi":"10.1016/j.memsci.2025.124055","DOIUrl":"10.1016/j.memsci.2025.124055","url":null,"abstract":"<div><div>In this work, a novel high-antifouling poly(vinylidene fluoride) (PVDF) composite membrane was synthesized via free radical polymerization by incorporating a pH-responsive poly(<em>N</em>-acryloyl-<span>l</span>-alanine) (poly(Ala-OH)) as a functional skin layer and 2-hydroxyethyl acrylate-terminated poly(styrene-alt-maleic anhydride) (SMA-HEA) as an amphiphilic linker for effective integration onto the PVDF substrate. FT-IR and XRD analyses confirmed the successful grafting of poly(Ala-OH) through the C<img>C bond of the linker, leading to a significant enhancement in membrane hydrophilicity. As a result, the modified membranes exhibited a hydrophilic surface. The pH-responsive behavior of the membrane was evident under alkaline conditions (pH = 11), where deprotonation of carboxylic acid groups induced a stronger negative surface charge, causing molecular chain expansion due to electrostatic repulsion. This structural adjustment further improved membrane hydrophilicity and anionic dye rejection. Consequently, the poly(Ala–OH)–modified PVDF membrane demonstrated higher and more stable flux during cyclic filtration tests under alkaline conditions. The results highlight the critical role of the poly(Ala-OH) layer's carboxylic acid groups and membrane charge variations in significantly enhancing overall hydrophilicity and antifouling performance, making it a promising solution for anionic dye filtration.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"727 ","pages":"Article 124055"},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Construction of Silica Nanoparticle Penetrant-doped TFN membranes for Enhanced Permeance Nanofiltration

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-04-01 DOI: 10.1016/j.memsci.2025.124059

Guodong Kong , Penglong Li , Xiaolei Cui , Zixi Kang , Hailing Guo , Svetlana Mintova

Constructing high-performance nanofiltration membranes requires maximizing water permeance while maintaining desirable rejection. Here, a thin-film nanocomposite (TFN) membrane with a filler penetrant-doped structure was designed for efficient desalination. Unlike conventional TFN membranes, the filler silica nanoparticles are exposed on the top of the polyamide layer, which further enhances the hydrophilicity and thus allows water to wet the membrane surface quickly. At the same time, the partially embedded silica nanoparticles create transportation channels for water molecules between silica and polyamide (PA) matrix. This stems from the moderate cross-linking between hydroxyl groups and chlorides on the silica surface, which builds water channels while avoiding large interfacial defects. As a result of the special doping, the NF membrane has a high water permeance, reaching an impressive value of 19.7 L m^-2h^-1 bar^-1, which is 95% higher than that of the conventional TFN membrane. Additionally, the membranes exhibited a Na₂SO₄ rejection exceeding 95%. In conclusion, this penetrant doping synthesis method provides a promising solution for the construction of high-permeance nanofiltration membranes.

{"title":"Construction of Silica Nanoparticle Penetrant-doped TFN membranes for Enhanced Permeance Nanofiltration","authors":"Guodong Kong , Penglong Li , Xiaolei Cui , Zixi Kang , Hailing Guo , Svetlana Mintova","doi":"10.1016/j.memsci.2025.124059","DOIUrl":"10.1016/j.memsci.2025.124059","url":null,"abstract":"<div><div>Constructing high-performance nanofiltration membranes requires maximizing water permeance while maintaining desirable rejection. Here, a thin-film nanocomposite (TFN) membrane with a filler penetrant-doped structure was designed for efficient desalination. Unlike conventional TFN membranes, the filler silica nanoparticles are exposed on the top of the polyamide layer, which further enhances the hydrophilicity and thus allows water to wet the membrane surface quickly. At the same time, the partially embedded silica nanoparticles create transportation channels for water molecules between silica and polyamide (PA) matrix. This stems from the moderate cross-linking between hydroxyl groups and chlorides on the silica surface, which builds water channels while avoiding large interfacial defects. As a result of the special doping, the NF membrane has a high water permeance, reaching an impressive value of 19.7 L m<sup>-2</sup>h<sup>-1</sup> bar<sup>-1</sup>, which is 95% higher than that of the conventional TFN membrane. Additionally, the membranes exhibited a Na<sub>2</sub>SO<sub>4</sub> rejection exceeding 95%. In conclusion, this penetrant doping synthesis method provides a promising solution for the construction of high-permeance nanofiltration membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124059"},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143768321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hyperbranched-type anion exchange membranes with electrostatic interactions for high performance anion exchange membrane water electrolysis

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-31 DOI: 10.1016/j.memsci.2025.124050

Soomin Jeon , Hyun Woo Kang , Kyungwhan Min , Wooseok Lee , Hyeonjun Maeng , Chi Hoon Park , Tae-Hyun Kim

Poly (aryl piperidinium) (PAP) has been widely employed in anion exchange membrane water electrolysis (AEMWE) because of its high ion exchange capacity and superior chemical stability. PAP-based anion exchange membranes (AEMs) equipped with hyperbranched structures have recently garnered significant attention as they contain multiple reactive sites, thus exhibiting high molecular weights and enhanced mechanical properties. Herein, hyperbranched poly (p-terphenyl N-methyl piperidinium) (QPTP) polymers using triphenylamine (b-Nm-QPTP) and triphenylmethane (b-Cm-QPTP) as hyperbranching units were fabricated and compared, notably with respect to the hyperbranching units. A linear QPTP polymer with no hyperbranched structures was also synthesized and used to fabricate a QPTP-based AEM for comparison. Both b-Nm-QPTP and b-Cm-QPTP achieved a higher viscosity (>1.4 dL/g) than the linear QPTP, and the b-Nm-QPTP- and b-Cm-QPTP-based AEMs exhibited enhanced mechanical properties (>30 MPa in terms of stress) compared to the QPTP-based AEM. Further, b-N5-QPTP, comprising 5 % triphenylamine, demonstrated the most pronounced microphase separation; this was attributed to nitrogen–water electrostatic interactions, as confirmed by molecular dynamics simulations. Thus, this membrane exhibited not only well-defined ion channels and improved ionic conductivity (157.68 mS/cm at 80 °C) but also remarkable chemical stability, with an ionic conductivity retention of over 96 % in 3 M KOH at 60 °C. Additionally, the AEMWE single-cell performance of b-N5-QPTP, 6.313 A/cm² at 2.0 V, was significantly higher than that of the commercial PiperION membrane (4.806 A/cm² at 2.0 V) and remained high (4.438 A/cm² at 2.0 V) even when non-noble metal catalysts were used, demonstrating its high feasibility for AEMWE applications.

{"title":"Hyperbranched-type anion exchange membranes with electrostatic interactions for high performance anion exchange membrane water electrolysis","authors":"Soomin Jeon , Hyun Woo Kang , Kyungwhan Min , Wooseok Lee , Hyeonjun Maeng , Chi Hoon Park , Tae-Hyun Kim","doi":"10.1016/j.memsci.2025.124050","DOIUrl":"10.1016/j.memsci.2025.124050","url":null,"abstract":"<div><div>Poly (aryl piperidinium) (PAP) has been widely employed in anion exchange membrane water electrolysis (AEMWE) because of its high ion exchange capacity and superior chemical stability. PAP-based anion exchange membranes (AEMs) equipped with hyperbranched structures have recently garnered significant attention as they contain multiple reactive sites, thus exhibiting high molecular weights and enhanced mechanical properties. Herein, hyperbranched poly (<em>p</em>-terphenyl <em>N</em>-methyl piperidinium) (QPTP) polymers using triphenylamine (b-Nm-QPTP) and triphenylmethane (b-Cm-QPTP) as hyperbranching units were fabricated and compared, notably with respect to the hyperbranching units. A linear QPTP polymer with no hyperbranched structures was also synthesized and used to fabricate a QPTP-based AEM for comparison. Both b-Nm-QPTP and b-Cm-QPTP achieved a higher viscosity (>1.4 dL/g) than the linear QPTP, and the b-Nm-QPTP- and b-Cm-QPTP-based AEMs exhibited enhanced mechanical properties (>30 MPa in terms of stress) compared to the QPTP-based AEM. Further, b-N5-QPTP, comprising 5 % triphenylamine, demonstrated the most pronounced microphase separation; this was attributed to nitrogen–water electrostatic interactions, as confirmed by molecular dynamics simulations. Thus, this membrane exhibited not only well-defined ion channels and improved ionic conductivity (157.68 mS/cm at 80 °C) but also remarkable chemical stability, with an ionic conductivity retention of over 96 % in 3 M KOH at 60 °C. Additionally, the AEMWE single-cell performance of b-N5-QPTP, 6.313 A/cm<sup>2</sup> at 2.0 V, was significantly higher than that of the commercial PiperION membrane (4.806 A/cm<sup>2</sup> at 2.0 V) and remained high (4.438 A/cm<sup>2</sup> at 2.0 V) even when non-noble metal catalysts were used, demonstrating its high feasibility for AEMWE applications.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124050"},"PeriodicalIF":8.4,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143768323","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

NH3 separation by ZnCl2 immobilized molten salt (IMS): Experimental and modeling

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-30 DOI: 10.1016/j.memsci.2025.124053

Moses Adejumo, Nicolena Fazio, Simona Liguori

The utilization of membrane-based separation demonstrates significant potential as a means to mitigate energy consumption and emissions in crucial industrial processes such as the Haber-Bosch process. This study systematically explored the performance of ZnCl₂ immobilized molten salt (IMS) membranes, both theoretically and experimentally, for separating NH₃ from N₂ and H₂. Experimentally, the separation characteristics of the ZnCl₂ IMS membrane supported on a 1 μm pore-sized wire mesh were determined when exposed to pure and mixed gases at 300 °C and atmospheric pressure. For the single gas permeation test, the NH₃ permeance was ∼218 GPU, with NH₃/N₂ and NH₃/H₂ ideal selectivities of >10⁷ and >10⁷ were achieved, respectively. In the case of binary mixtures, NH₃ permeance within the range of 1800–2000 GPU was attained at a feed NH₃ partial pressure of ∼5 kPa. The membrane was reasonably stable for ≥640 h under different feed mixtures. The theoretical component examined the transport mechanisms of NH₃ across the ZnCl₂ IMS membranes and employed a mathematical model initially introduced by Xu et al. [J. Chem. Eng. 460 (2023) 141728]. The mathematical model was fitted to experimentally measured NH₃ fluxes as a function of the NH₃ partial pressure (∼10–100 kPa) and membrane thicknesses. The mean absolute percentage error (MAPE) between the model and experimental data was less than 3%. In particular, the model was used to deduce the kinetic and thermodynamic parameters related to the permeation of NH₃ through the membrane.

{"title":"NH3 separation by ZnCl2 immobilized molten salt (IMS): Experimental and modeling","authors":"Moses Adejumo, Nicolena Fazio, Simona Liguori","doi":"10.1016/j.memsci.2025.124053","DOIUrl":"10.1016/j.memsci.2025.124053","url":null,"abstract":"<div><div>The utilization of membrane-based separation demonstrates significant potential as a means to mitigate energy consumption and emissions in crucial industrial processes such as the Haber-Bosch process. This study systematically explored the performance of ZnCl<sub>2</sub> immobilized molten salt (IMS) membranes, both theoretically and experimentally, for separating NH<sub>3</sub> from N<sub>2</sub> and H<sub>2</sub>. Experimentally, the separation characteristics of the ZnCl<sub>2</sub> IMS membrane supported on a 1 μm pore-sized wire mesh were determined when exposed to pure and mixed gases at 300 °C and atmospheric pressure. For the single gas permeation test, the NH<sub>3</sub> permeance was ∼218 GPU, with NH<sub>3</sub>/N<sub>2</sub> and NH<sub>3</sub>/H<sub>2</sub> ideal selectivities of >10<sup>7</sup> and >10<sup>7</sup> were achieved, respectively. In the case of binary mixtures, NH<sub>3</sub> permeance within the range of 1800–2000 GPU was attained at a feed NH<sub>3</sub> partial pressure of ∼5 kPa. The membrane was reasonably stable for ≥640 h under different feed mixtures. The theoretical component examined the transport mechanisms of NH<sub>3</sub> across the ZnCl<sub>2</sub> IMS membranes and employed a mathematical model initially introduced by Xu et al. [J. Chem. Eng. 460 (2023) 141728]. The mathematical model was fitted to experimentally measured NH<sub>3</sub> fluxes as a function of the NH<sub>3</sub> partial pressure (∼10–100 kPa) and membrane thicknesses. The mean absolute percentage error (MAPE) between the model and experimental data was less than 3%. In particular, the model was used to deduce the kinetic and thermodynamic parameters related to the permeation of NH<sub>3</sub> through the membrane.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124053"},"PeriodicalIF":8.4,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Evaluation of the stability of β-ketoenamine-Type covalent organic framework membranes in organic solvent

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-30 DOI: 10.1016/j.memsci.2025.124052

Xuan Wang , Jiaojiao Duan , Weiliang Li , Xiaoli Wu , Yong Wang , Mingjie Wei , Yifan Li , Runnan Zhang , Jingtao Wang

Covalent organic framework (COF) materials hold significant promise for membrane technology due to their precisely defined porous structures and tunable functionalities. However, the stability of COF membranes in organic solvents, critical for long-term operation, has seldom been studied and remains unclear. This study synthesizes three β-ketoenamine type COF membranes with different amounts of sulfonate groups via vacuum-assisted assembly and systematically evaluates their stability in four typical organic solvents (alcohol, ketone, ester, and alkane), respectively. We investigated the time-dependent membrane morphologies, thickness swelling, and long-term organic solvent nanofiltration (OSN) performance within a period of up to 180 days. Although the COF membranes suffer from a certain degree of structural change and permeance decline during the initial testing period, they can finally achieve quite stable separation performance. The effects of solvent type and the number of -SO₃H groups on membrane stability are systematically discussed. Based on the evaluation methods adopted in this study, the prospects of COF membranes for long-time application in organic solvent can be highlighted, but some critical problems are also raised. We also investigate the swelling behavior under harsh conditions (e.g. elevated temperature, strong acids, and alkalis) to accelerate the swelling process, which is found to enable fast and effective evaluation of the long-term stability.

{"title":"Evaluation of the stability of β-ketoenamine-Type covalent organic framework membranes in organic solvent","authors":"Xuan Wang , Jiaojiao Duan , Weiliang Li , Xiaoli Wu , Yong Wang , Mingjie Wei , Yifan Li , Runnan Zhang , Jingtao Wang","doi":"10.1016/j.memsci.2025.124052","DOIUrl":"10.1016/j.memsci.2025.124052","url":null,"abstract":"<div><div>Covalent organic framework (COF) materials hold significant promise for membrane technology due to their precisely defined porous structures and tunable functionalities. However, the stability of COF membranes in organic solvents, critical for long-term operation, has seldom been studied and remains unclear. This study synthesizes three β-ketoenamine type COF membranes with different amounts of sulfonate groups via vacuum-assisted assembly and systematically evaluates their stability in four typical organic solvents (alcohol, ketone, ester, and alkane), respectively. We investigated the time-dependent membrane morphologies, thickness swelling, and long-term organic solvent nanofiltration (OSN) performance within a period of up to 180 days. Although the COF membranes suffer from a certain degree of structural change and permeance decline during the initial testing period, they can finally achieve quite stable separation performance. The effects of solvent type and the number of -SO<sub>3</sub>H groups on membrane stability are systematically discussed. Based on the evaluation methods adopted in this study, the prospects of COF membranes for long-time application in organic solvent can be highlighted, but some critical problems are also raised. We also investigate the swelling behavior under harsh conditions (e.g. elevated temperature, strong acids, and alkalis) to accelerate the swelling process, which is found to enable fast and effective evaluation of the long-term stability.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124052"},"PeriodicalIF":8.4,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143791503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

PIM-1 membrane incorporated cPIM-1 grafted PP-DETA for high-efficiency CO2/N2 separation

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-28 DOI: 10.1016/j.memsci.2025.124051

Shuangqi Song, Hong Li, Jingde Li, Yanqin Yang

Mixed-matrix membranes (MMMs), developed through the combination of solid fillers with polymer matrices, represent an effective approach addressing the persistent challenge of balancing permeability and selectivity in polymer membrane. Diethylenetriamine-functionalized porous material of PP-DETA, which is synthesized from porous organic polymer of PP via one-step diethylenetriamine grafting, is an ideal material for MMMs production. However, designing and optimizing PP-DETA for high-performance CO₂ separation membranes remains a challenge. Herein, we develop an improved PP-DETA material, designated as PP-DETA-cPIM-1, by covalently attaching a carboxylated polymer of intrinsic microporosity (cPIM-1) network layer onto the PP-DETA surface. Membranes prepared from this PP-DETA-cPIM-1 filler and PIM-1 matrix demonstrate enhanced interfacial adhesion and stronger mechanical properties in comparison to the counterparts with the same loading of PP-DETA. The incorporation of PP-DETA-cPIM-1 into MMMs establishes an enhanced filler/polymer interface that facilitates the selective transport of CO₂ through the filler, while simultaneously improving membrane stability and suppressing physical aging. Specifically, with 5 wt% loading of PP-DETA-cPIM-1 filler, the MMM is able to enhance the CO₂/N₂ selectivity and CO₂ permeability by 52.3 % and 25.3 %, respectively, exceeding the upper bound established in 2008. Furthermore, PP-DETA-cPIM-1/PIM-1 MMMs display superior anti-aging ability for 180 days of aging.

{"title":"PIM-1 membrane incorporated cPIM-1 grafted PP-DETA for high-efficiency CO2/N2 separation","authors":"Shuangqi Song, Hong Li, Jingde Li, Yanqin Yang","doi":"10.1016/j.memsci.2025.124051","DOIUrl":"10.1016/j.memsci.2025.124051","url":null,"abstract":"<div><div>Mixed-matrix membranes (MMMs), developed through the combination of solid fillers with polymer matrices, represent an effective approach addressing the persistent challenge of balancing permeability and selectivity in polymer membrane. Diethylenetriamine-functionalized porous material of PP-DETA, which is synthesized from porous organic polymer of PP via one-step diethylenetriamine grafting, is an ideal material for MMMs production. However, designing and optimizing PP-DETA for high-performance CO<sub>2</sub> separation membranes remains a challenge. Herein, we develop an improved PP-DETA material, designated as PP-DETA-cPIM-1, by covalently attaching a carboxylated polymer of intrinsic microporosity (cPIM-1) network layer onto the PP-DETA surface. Membranes prepared from this PP-DETA-cPIM-1 filler and PIM-1 matrix demonstrate enhanced interfacial adhesion and stronger mechanical properties in comparison to the counterparts with the same loading of PP-DETA. The incorporation of PP-DETA-cPIM-1 into MMMs establishes an enhanced filler/polymer interface that facilitates the selective transport of CO<sub>2</sub> through the filler, while simultaneously improving membrane stability and suppressing physical aging. Specifically, with 5 wt% loading of PP-DETA-cPIM-1 filler, the MMM is able to enhance the CO<sub>2</sub>/N<sub>2</sub> selectivity and CO<sub>2</sub> permeability by 52.3 % and 25.3 %, respectively, exceeding the upper bound established in 2008. Furthermore, PP-DETA-cPIM-1/PIM-1 MMMs display superior anti-aging ability for 180 days of aging.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"727 ","pages":"Article 124051"},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Surfactants intervened construction of NF membranes for lithium extraction in high Mg2+/Li+ ratio and high concentration environments

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-28 DOI: 10.1016/j.memsci.2025.124048

Rui Jia , Hua-Xiang Li , Zhen-Liang Xu , Xiao-Gang Jin , Liu-Kun Wu , Hui-Hui Ping , Xiao-Hua Ma , Sun-Jie Xu

Nanofiltration (NF) membranes offer notable benefits for Li⁺/Mg²⁺ separation, but their efficiency tends to diminish when exposed to mixed salt solutions with elevated Mg²⁺ concentrations or high Mg²⁺/Li⁺ ratios (MLR), restricting their practical applications. This study employed the surfactant-assisted interfacial polymerization (SIAIP) method to incorporate sodium dodecyl sulfate (SDS) and dodecyl phosphate (DDP), leading to the creation of two NF membranes with opposite surface charge characteristics. SDS promoted the trans-interfacial diffusion of the amine monomer while simultaneously limiting its escape from the bulk-phase solution, which was crucial for developing positively charged membranes. Conversely, DDP predominantly influenced the interfacial diffusion of the amine monomer, resulting in a membrane with a reduced pore size and a negatively charged active layer. SIAIP-DDP membranes exhibited excellent stability (S _{Li, Mg} > 110) in environments with high MLR and Mg²⁺ concentrations, highlighting their potential for application in harsh salt-lake brine. This work presents a detailed mechanistic analysis of the surfactant-induced interfacial polymerization process, offering new insights into the efficient separation of Li⁺/Mg²⁺ under high MLR and high concentration conditions.

{"title":"Surfactants intervened construction of NF membranes for lithium extraction in high Mg2+/Li+ ratio and high concentration environments","authors":"Rui Jia , Hua-Xiang Li , Zhen-Liang Xu , Xiao-Gang Jin , Liu-Kun Wu , Hui-Hui Ping , Xiao-Hua Ma , Sun-Jie Xu","doi":"10.1016/j.memsci.2025.124048","DOIUrl":"10.1016/j.memsci.2025.124048","url":null,"abstract":"<div><div>Nanofiltration (NF) membranes offer notable benefits for Li<sup>+</sup>/Mg<sup>2+</sup> separation, but their efficiency tends to diminish when exposed to mixed salt solutions with elevated Mg<sup>2+</sup> concentrations or high Mg<sup>2+</sup>/Li<sup>+</sup> ratios (MLR), restricting their practical applications. This study employed the surfactant-assisted interfacial polymerization (SIAIP) method to incorporate sodium dodecyl sulfate (SDS) and dodecyl phosphate (DDP), leading to the creation of two NF membranes with opposite surface charge characteristics. SDS promoted the <em>trans</em>-interfacial diffusion of the amine monomer while simultaneously limiting its escape from the bulk-phase solution, which was crucial for developing positively charged membranes. Conversely, DDP predominantly influenced the interfacial diffusion of the amine monomer, resulting in a membrane with a reduced pore size and a negatively charged active layer. SIAIP-DDP membranes exhibited excellent stability (S <sub>Li, Mg</sub> > 110) in environments with high MLR and Mg<sup>2+</sup> concentrations, highlighting their potential for application in harsh salt-lake brine. This work presents a detailed mechanistic analysis of the surfactant-induced interfacial polymerization process, offering new insights into the efficient separation of Li<sup>+</sup>/Mg<sup>2+</sup> under high MLR and high concentration conditions.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124048"},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Greener TEAMs: Tethered electrolyte active-layer membranes produced by surface-initiated free radical polymerization

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-28 DOI: 10.1016/j.memsci.2025.124049

Elnur Jabiyev, Mohammad Hossein Mehdi Pour, Cassandra J. Porter

As the world shifts toward sustainability, the recovery of valuable elements involved in energy storage and production, such as lithium and uranium, has gained increasing importance. Nanofiltration (NF) membranes are garnering attention as promising candidates for addressing complex separations involving species with similar chemical properties, sizes, and charges. Tethered electrolyte active-layer membranes (TEAMs) are a notable development within this realm. Production of TEAMs previously involved surface-initiated atom transfer radical polymerization (SI-ATRP) to grow neutral polymer precursors from an ultrafiltration cellulose substrate and subsequently modify repeat unit sidechains into ionizable groups. However, SI-ATRP uses harsh organic solvents, metal catalysts, and multistep synthesis. In this study, we demonstrate a more environmentally sustainable and simplified alternative by utilizing surface-initiated free radical polymerization (SI-FRP) to synthesize greener TEAMs. Monomers of methacroylcholine chloride, acrylic acid, and sodium 4-vinylbenzenesulfonate were grafted from the surface of commercial ultrafiltration cellulose membranes. Both positive and negative TEAMs rejected more than 95 % of divalent salts and 80 % of monovalent salts, with permeability ranging from approximately 4 to 8 Lm⁻²h⁻¹bar⁻¹. In addition, monovalent selectivity was probed using varied proportions of monovalent versus divalent co-ions. SI-FRP-TEAMs exhibited monovalent over divalent cation selectivity of ∼8 and anion selectivity of ∼9 with 75 % divalent co-ions. This study is an essential step in positioning TEAMs as a more accessible platform for fundamental membrane transport exploration and development of ion selective membranes for resource recovery.

{"title":"Greener TEAMs: Tethered electrolyte active-layer membranes produced by surface-initiated free radical polymerization","authors":"Elnur Jabiyev, Mohammad Hossein Mehdi Pour, Cassandra J. Porter","doi":"10.1016/j.memsci.2025.124049","DOIUrl":"10.1016/j.memsci.2025.124049","url":null,"abstract":"<div><div>As the world shifts toward sustainability, the recovery of valuable elements involved in energy storage and production, such as lithium and uranium, has gained increasing importance. Nanofiltration (NF) membranes are garnering attention as promising candidates for addressing complex separations involving species with similar chemical properties, sizes, and charges. Tethered electrolyte active-layer membranes (TEAMs) are a notable development within this realm. Production of TEAMs previously involved surface-initiated atom transfer radical polymerization (SI-ATRP) to grow neutral polymer precursors from an ultrafiltration cellulose substrate and subsequently modify repeat unit sidechains into ionizable groups. However, SI-ATRP uses harsh organic solvents, metal catalysts, and multistep synthesis. In this study, we demonstrate a more environmentally sustainable and simplified alternative by utilizing surface-initiated free radical polymerization (SI-FRP) to synthesize greener TEAMs. Monomers of methacroylcholine chloride, acrylic acid, and sodium 4-vinylbenzenesulfonate were grafted from the surface of commercial ultrafiltration cellulose membranes. Both positive and negative TEAMs rejected more than 95 % of divalent salts and 80 % of monovalent salts, with permeability ranging from approximately 4 to 8 Lm<sup>−2</sup>h<sup>−1</sup>bar<sup>−1</sup>. In addition, monovalent selectivity was probed using varied proportions of monovalent versus divalent co-ions. SI-FRP-TEAMs exhibited monovalent over divalent cation selectivity of ∼8 and anion selectivity of ∼9 with 75 % divalent co-ions. This study is an essential step in positioning TEAMs as a more accessible platform for fundamental membrane transport exploration and development of ion selective membranes for resource recovery.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124049"},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0