Pub Date : 2025-12-29DOI: 10.1016/j.memsci.2025.125113
Abdiel Lugo , Tayia L. Oddonetto , Mohammed Fuwad Ahmed , Punhasa S. Senanayake , Zachary Stoll , Neil Moe , John Barber , Huiyao Wang , Pei Xu
This work presents a comprehensive modeling framework for designing and optimizing bipolar membrane electrodialysis (BMED) systems, aiming to recover resources from hypersaline brines. The model integrates batch and continuous system operations, accounting for membrane-specific transport properties, dynamic or fixed current control, and stack-scale interactions under high salinity conditions. Experimental validation demonstrated strong agreement in acid and base production and electrical performance, following adjustments to proton diffusion through anion exchange membranes. Full-scale continuous modeling evaluated dynamic and fixed current strategies, revealing trade-offs in energy efficiency, stack requirements, and proton leakage mitigation. A final zero liquid discharge scenario integrated BMED into a closed-loop system with brine concentrators, demonstrating significantly enhanced water recovery, reduced brine disposal volume, and recovery of valuable chemicals. This study advances scalable BMED modeling and system optimization, providing a crucial tool for sustainable management of hypersaline brines.
{"title":"Bipolar membrane electrodialysis for acid and base production in high salinity desalination brine – dynamic modeling and system design evaluation","authors":"Abdiel Lugo , Tayia L. Oddonetto , Mohammed Fuwad Ahmed , Punhasa S. Senanayake , Zachary Stoll , Neil Moe , John Barber , Huiyao Wang , Pei Xu","doi":"10.1016/j.memsci.2025.125113","DOIUrl":"10.1016/j.memsci.2025.125113","url":null,"abstract":"<div><div>This work presents a comprehensive modeling framework for designing and optimizing bipolar membrane electrodialysis (BMED) systems, aiming to recover resources from hypersaline brines. The model integrates batch and continuous system operations, accounting for membrane-specific transport properties, dynamic or fixed current control, and stack-scale interactions under high salinity conditions. Experimental validation demonstrated strong agreement in acid and base production and electrical performance, following adjustments to proton diffusion through anion exchange membranes. Full-scale continuous modeling evaluated dynamic and fixed current strategies, revealing trade-offs in energy efficiency, stack requirements, and proton leakage mitigation. A final zero liquid discharge scenario integrated BMED into a closed-loop system with brine concentrators, demonstrating significantly enhanced water recovery, reduced brine disposal volume, and recovery of valuable chemicals. This study advances scalable BMED modeling and system optimization, providing a crucial tool for sustainable management of hypersaline brines.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"742 ","pages":"Article 125113"},"PeriodicalIF":9.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.memsci.2025.125112
Le Wang , Xiaoyu Li , Jiejun Zeng , Yunji Xie , Di Liu , Jiaran Song , Yuanlong Wu , Zhe Wang
Anion exchange membranes (AEMs) serve as pivotal component in anion exchange membrane fuel cell (AEMFC) systems, where achieving simultaneous optimization of ionic conductivity, dimensional stability, and alkaline stability represents a critical technological challenge. Through rational molecular design, a series of branched poly(aryl piperidine) AEMs (QAPTP-Px) is developed by incorporating conjugated triphenylene (Tp) moieties as three-dimensional branching units. The incorporation of branching sites effectively restricts chain segment mobility, resulting in branched membranes with lower water uptake and superior swelling resistance compared to linear poly(aryl piperidine) AEMs (QAPTP-P0). Despite their reduced water uptakes, the branched membranes maintain satisfactory conductivity due to their well-developed phase-separated morphology. The conductivity of the QAPTP-P1.5 membrane with a moderate degree of branching reaches 120.74 mS cm−1 at 80 °C, exceeding the conductivity of the linear membrane. Notably, the QAPTP-P1.5 membrane demonstrates exceptional chemical stability: it retains 97.14 % of its initial mass after 144 h in Fenton's reagent at 80 °C, while maintaining over 94 % of its original conductivity following 1500 h of immersion in 2 M NaOH. Furthermore, the QAPTP-P1.5 membrane exhibits considerable fuel cell performance, achieving a peak power density of 426 mW cm−2 at 80 °C. Remarkably, no voltage decay is observed during a 60 h stability test under a constant current of 0.1 A cm−2. These results highlight the ability of this branched membrane series to effectively balance conductivity and stability, offering valuable insights for the design of next-generation H2–O2 fuel cell membranes.
阴离子交换膜（AEMs）是阴离子交换膜燃料电池（AEMFC）系统的关键部件，同时实现离子电导率、尺寸稳定性和碱性稳定性的优化是一个关键的技术挑战。通过合理的分子设计，以共轭三苯基（Tp）为三维支链单元，开发了一系列支链聚芳基哌啶AEMs （QAPTP-Px）。与线性聚芳基哌啶AEMs （QAPTP-P0）相比，分支位点的掺入有效地限制了链段的迁移，从而使支链膜具有更低的吸水性和更强的抗膨胀性。尽管它们的水摄取减少，支膜保持令人满意的导电性，由于其发达的相分离形态。中等分支度的QAPTP-P1.5膜在80℃时的电导率达到了120.74 mS cm−1，超过了线性膜的电导率。值得注意的是，QAPTP-P1.5膜表现出优异的化学稳定性：在80°C的Fenton试剂中浸泡144小时后，它保持了97.14%的初始质量，而在2 M NaOH中浸泡1500小时后，它保持了94%以上的原始导电性。此外，QAPTP-P1.5膜表现出相当好的燃料电池性能，在80°C下达到426 mW cm - 2的峰值功率密度。值得注意的是，在0.1 a cm−2的恒定电流下，在60 h的稳定性测试中没有观察到电压衰减。这些结果突出了分支膜系列有效平衡导电性和稳定性的能力，为下一代H2-O2燃料电池膜的设计提供了有价值的见解。
{"title":"Branching-induced dimensional stability and conductivity balance in anion exchange membranes for fuel cells","authors":"Le Wang , Xiaoyu Li , Jiejun Zeng , Yunji Xie , Di Liu , Jiaran Song , Yuanlong Wu , Zhe Wang","doi":"10.1016/j.memsci.2025.125112","DOIUrl":"10.1016/j.memsci.2025.125112","url":null,"abstract":"<div><div>Anion exchange membranes (AEMs) serve as pivotal component in anion exchange membrane fuel cell (AEMFC) systems, where achieving simultaneous optimization of ionic conductivity, dimensional stability, and alkaline stability represents a critical technological challenge. Through rational molecular design, a series of branched poly(aryl piperidine) AEMs (QAPTP-Px) is developed by incorporating conjugated triphenylene (Tp) moieties as three-dimensional branching units. The incorporation of branching sites effectively restricts chain segment mobility, resulting in branched membranes with lower water uptake and superior swelling resistance compared to linear poly(aryl piperidine) AEMs (QAPTP-P0). Despite their reduced water uptakes, the branched membranes maintain satisfactory conductivity due to their well-developed phase-separated morphology. The conductivity of the QAPTP-P1.5 membrane with a moderate degree of branching reaches 120.74 mS cm<sup>−1</sup> at 80 °C, exceeding the conductivity of the linear membrane. Notably, the QAPTP-P1.5 membrane demonstrates exceptional chemical stability: it retains 97.14 % of its initial mass after 144 h in Fenton's reagent at 80 °C, while maintaining over 94 % of its original conductivity following 1500 h of immersion in 2 M NaOH. Furthermore, the QAPTP-P1.5 membrane exhibits considerable fuel cell performance, achieving a peak power density of 426 mW cm<sup>−2</sup> at 80 °C. Remarkably, no voltage decay is observed during a 60 h stability test under a constant current of 0.1 A cm<sup>−2</sup>. These results highlight the ability of this branched membrane series to effectively balance conductivity and stability, offering valuable insights for the design of next-generation H<sub>2</sub>–O<sub>2</sub> fuel cell membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125112"},"PeriodicalIF":9.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.memsci.2025.125109
Qiang Wu , Xiao Liang , Hongli Kang , Feifei Huang , Shichao Liu , Ruirun Chen , Jingjie Guo
Three alloys, Nb35Mo5Ti30Co25Fe5, Nb43Mo5Ti27Co20Fe5, and Nb51Mo5Ti23Co16Fe5, were investigated theoretically and experimentally, and hydrogen absorption and hydrogen permeation were analyzed based on the chemical potential to extend Sieverts' law and Fick's first law from dilute hydrogen conditions to non-dilute hydrogen conditions. The equilibrium hydrogen pressure and equilibrium concentration relationship graph ∼, and the normalized hydrogen permeation flux and relative concentration relationship graph Jd∼ show a clear linear relationship, from which the interaction parameter Ω of the hydrogen atoms with the alloy and the hydrogen diffusion mobility B were calculated; The interaction parameter and hydrogen diffusion mobility are temperature-dependent and are unaffected by variations in hydrogen concentration. Hydrogen permeable experiments and hydrogen embrittlement experiments demonstrate that Nb35Mo5Ti30Co25Fe5, Nb43Mo5Ti27Co20Fe5, and Nb51Mo5Ti23Co16Fe5 alloy membranes exhibit improved hydrogen permeability and resistance to hydrogen embrittlement compared to the original alloy. Among them, Nb35Mo5Ti30Co25Fe5 has excellent hydrogen embrittlement resistance and hydrogen permeability. It does not fail after 120 h of long-term hydrogen permeation at 673 K. The normalized hydrogen permeation flux under the same condition is 1.22 and 1.18 times that of Pd and Pd–Ag, respectively, making it a promising material to replace Pd and its alloys.
对Nb35Mo5Ti30Co25Fe5、Nb43Mo5Ti27Co20Fe5和Nb51Mo5Ti23Co16Fe5三种合金进行了理论和实验研究，并基于化学势对Sieverts定律和Fick第一定律从稀氢条件推广到非稀氢条件下的吸氢和氢渗透进行了分析。平衡氢压力和平衡浓度关系图ln(P/r) ~(1‐r)2，归一化氢渗透通量和相对浓度关系图Jd ~ C ln（Pu/Pd）呈现明确的线性关系，由此计算氢原子与合金的相互作用参数Ω和氢扩散迁移率B；相互作用参数和氢扩散迁移率与温度有关，不受氢浓度变化的影响。氢透性实验和氢脆实验表明，Nb35Mo5Ti30Co25Fe5、Nb43Mo5Ti27Co20Fe5和Nb51Mo5Ti23Co16Fe5合金膜的氢透性和抗氢脆性能均优于原合金。其中Nb35Mo5Ti30Co25Fe5具有优异的抗氢脆性和氢渗透性。在673 K下长期氢渗透120 h后，它不会失效。在相同条件下，归一化氢渗透通量分别是Pd和Pd - ag的1.22倍和1.18倍，是替代Pd及其合金的理想材料。
{"title":"Theoretical and experimental analysis of Nb-based alloy membranes at non-dilute hydrogen concentration","authors":"Qiang Wu , Xiao Liang , Hongli Kang , Feifei Huang , Shichao Liu , Ruirun Chen , Jingjie Guo","doi":"10.1016/j.memsci.2025.125109","DOIUrl":"10.1016/j.memsci.2025.125109","url":null,"abstract":"<div><div>Three alloys, Nb<sub>35</sub>Mo<sub>5</sub>Ti<sub>30</sub>Co<sub>25</sub>Fe<sub>5</sub>, Nb<sub>43</sub>Mo<sub>5</sub>Ti<sub>27</sub>Co<sub>20</sub>Fe<sub>5</sub>, and Nb<sub>51</sub>Mo<sub>5</sub>Ti<sub>23</sub>Co<sub>16</sub>Fe<sub>5</sub>, were investigated theoretically and experimentally, and hydrogen absorption and hydrogen permeation were analyzed based on the chemical potential to extend Sieverts' law and Fick's first law from dilute hydrogen conditions to non-dilute hydrogen conditions. The equilibrium hydrogen pressure and equilibrium concentration relationship graph <span><math><mrow><mi>ln</mi><mrow><mo>(</mo><mrow><msqrt><mi>P</mi></msqrt><mo>/</mo><mi>r</mi></mrow><mo>)</mo></mrow></mrow></math></span> ∼<span><math><mrow><msup><mrow><mo>(</mo><mrow><mn>1</mn><mo>‐</mo><mi>r</mi></mrow><mo>)</mo></mrow><mn>2</mn></msup></mrow></math></span>, and the normalized hydrogen permeation flux and relative concentration relationship graph <em>Jd</em>∼ <span><math><mrow><mover><mi>C</mi><mo>‾</mo></mover><mspace></mspace><mi>ln</mi><mrow><mo>(</mo><mrow><msub><mi>P</mi><mi>u</mi></msub><mo>/</mo><msub><mi>P</mi><mi>d</mi></msub></mrow><mo>)</mo></mrow></mrow></math></span> show a clear linear relationship, from which the interaction parameter Ω of the hydrogen atoms with the alloy and the hydrogen diffusion mobility <em>B</em> were calculated; The interaction parameter and hydrogen diffusion mobility are temperature-dependent and are unaffected by variations in hydrogen concentration. Hydrogen permeable experiments and hydrogen embrittlement experiments demonstrate that Nb35Mo5Ti30Co25Fe5, Nb43Mo5Ti27Co20Fe5, and Nb51Mo5Ti23Co16Fe5 alloy membranes exhibit improved hydrogen permeability and resistance to hydrogen embrittlement compared to the original alloy. Among them, Nb<sub>35</sub>Mo<sub>5</sub>Ti<sub>30</sub>Co<sub>25</sub>Fe<sub>5</sub> has excellent hydrogen embrittlement resistance and hydrogen permeability. It does not fail after 120 h of long-term hydrogen permeation at 673 K. The normalized hydrogen permeation flux under the same condition is 1.22 and 1.18 times that of Pd and Pd–Ag, respectively, making it a promising material to replace Pd and its alloys.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"742 ","pages":"Article 125109"},"PeriodicalIF":9.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.memsci.2025.125108
Aiwen Zhang , Kecheng Guan , Shaochong Cao , Zhan Li , Liheng Dai , Mengyang Hu , Pengfei Zhang , Xueru Yan , Yanyan Liu , Jie Shen , Hideto Matsuyama
Separating polar organic solvent mixtures remains a major challenge due to strong intermolecular interactions and molecular similarity. Organic solvent reverse osmosis (OSRO) offers an energy-efficient alternative to distillation but is limited by the lack of membranes with homogeneous polar pores. Here, we report a surfactant-monomer co-assembly strategy between polyethyleneimine bearing polar functional groups and sodium dodecyl sulfate at a critical polymer saturation point, enabling precise control of monomer distribution and reaction kinetics to regulate interfacial polymerization for the formation of uniform, ultrathin polyamide OSRO membranes. The resulting membranes exhibit well defined polar pores and achieve outstanding performance in preferentially permeating methanol over toluene, with flux of 11–48 kg m−2 h−1 and separation factors of 48–128 under 3–7 MPa. These results demonstrate the necessity of homogeneous polar pores in achieving precise polar solvents separation, establishing self-assembly-regulated IP as a powerful platform for advanced OSRO membrane design.
分离极性有机溶剂混合物仍然是主要的挑战，由于强分子间相互作用和分子相似性。有机溶剂反渗透（OSRO）为蒸馏提供了一种节能的替代方法，但由于缺乏具有均匀极性孔的膜而受到限制。在这里，我们报告了一种表面活性剂-单体共聚策略，在具有极性官能团的聚乙烯亚胺和十二烷基硫酸钠之间的临界聚合物饱和点，能够精确控制单体分布和反应动力学，以调节界面聚合，形成均匀的超薄聚酰胺OSRO膜。在3-7 MPa条件下，膜的通量为11-48 kg m−2 h−1，分离系数为48-128，具有良好的极性孔，优先渗透甲醇而非甲苯的性能。这些结果证明了均匀极性孔在实现精确极性溶剂分离中的必要性，建立了自组装调节的IP作为先进OSRO膜设计的强大平台。
{"title":"Interfacial polymerization regulated by self-assembled monomer complexes for organic solvent reverse osmosis membranes","authors":"Aiwen Zhang , Kecheng Guan , Shaochong Cao , Zhan Li , Liheng Dai , Mengyang Hu , Pengfei Zhang , Xueru Yan , Yanyan Liu , Jie Shen , Hideto Matsuyama","doi":"10.1016/j.memsci.2025.125108","DOIUrl":"10.1016/j.memsci.2025.125108","url":null,"abstract":"<div><div>Separating polar organic solvent mixtures remains a major challenge due to strong intermolecular interactions and molecular similarity. Organic solvent reverse osmosis (OSRO) offers an energy-efficient alternative to distillation but is limited by the lack of membranes with homogeneous polar pores. Here, we report a surfactant-monomer co-assembly strategy between polyethyleneimine bearing polar functional groups and sodium dodecyl sulfate at a critical polymer saturation point, enabling precise control of monomer distribution and reaction kinetics to regulate interfacial polymerization for the formation of uniform, ultrathin polyamide OSRO membranes. The resulting membranes exhibit well defined polar pores and achieve outstanding performance in preferentially permeating methanol over toluene, with flux of 11–48 kg m<sup>−2</sup> h<sup>−1</sup> and separation factors of 48–128 under 3–7 MPa. These results demonstrate the necessity of homogeneous polar pores in achieving precise polar solvents separation, establishing self-assembly-regulated IP as a powerful platform for advanced OSRO membrane design.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125108"},"PeriodicalIF":9.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-28DOI: 10.1016/j.memsci.2025.125107
Xuewu Zhu , Feiyue Ge , Liping Qiu , Hong Peng , Fanduo Meng , Langming Bai , Feiyong Chen , Daliang Xu , Daoji Wu , Bin Liu
Nanofiltration (NF) plays a critical role in advanced water treatment; however, the performance of conventional polyamide (PA) membranes is fundamentally limited by the permeance–selectivity trade-off, a consequence of the densely cross-linked network formed via trimesoyl chloride (TMC) and piperazine (PIP) reaction. To address this issue, this study presents a molecular-level engineering approach that redesigns the PA network architecture by employing a competitive interfacial polymerization (IP) process using mixed acyl chloride monomers. Specifically, isophthaloyl chloride (IPC) is introduced as a crosslinking modulator that competitively restrains the over-crosslinking of TMC and acts as a chain extender to enhance the flexibility of the polymer matrix. Density functional theory (DFT) calculations revealed that the distinct electrostatic potential differences among monomers drive this precise regulation, resulting in a hybrid network with optimized fractional free volume. This rationally tailored structure led to a significant improvement in membrane performance, exhibiting a high pure water permeance of 18.9 L m−2 h−1 bar−1 (2.5 times that of the pristine PA-TMC membrane) without compromising selectivity. Furthermore, the engineered membrane featured a highly electronegative and carboxyl-rich surface, which strengthens membrane–ion interactions via a synergistic surface complexation–charge shielding mechanism, thereby creating elevated ion transport barriers and enabling superior divalent ion separation (e.g., 82.9 % for MgCl2 and >99.0 % for Na2SO4). Efficient removal of both natural organic matter and persistent negatively charged contaminants was achieved, with rejection rates exceeding 95 % for PFOA and reaching 99.5 % for large-molecule PFAS (e.g., PFODA). This study introduces a method to control polymer network formation using competitive reaction kinetics, yielding high-performance separation membranes while enhancing the understanding of the structure-property relationships in PA films for environmental applications.
纳滤在深度水处理中起着至关重要的作用；然而，传统聚酰胺（PA）膜的性能从根本上受到渗透-选择性权衡的限制，这是由三甲酰氯（TMC）和哌嗪（PIP）反应形成的密集交联网络的结果。为了解决这个问题，本研究提出了一种分子水平的工程方法，通过使用混合酰氯单体采用竞争性界面聚合（IP）工艺重新设计PA网络结构。具体来说，异苯甲酰氯（IPC）作为一种交联调节剂被引入，它可以竞争性地抑制TMC的过交联，并作为扩链剂增强聚合物基体的柔韧性。密度泛函理论（DFT）计算表明，单体之间明显的静电电位差驱动了这种精确的调节，从而形成了具有优化分数自由体积的混合网络。这种合理定制的结构显著改善了膜的性能，表现出18.9 L m−2 h−1 bar−1的高纯水渗透率（是原始PA-TMC膜的2.5倍），而不影响选择性。此外，工程膜具有高度电负性和富含羧基的表面，通过协同表面络合-电荷屏蔽机制加强了膜与离子的相互作用，从而提高了离子传输屏障，实现了优异的二价离子分离（例如，MgCl2和Na2SO4的分离率分别为82.9%和99.0%）。实现了对天然有机物和持久性带负电荷污染物的有效去除，对PFOA的去除率超过95%，对大分子PFAS（如PFODA）的去除率达到99.5%。本研究介绍了一种利用竞争反应动力学控制聚合物网络形成的方法，生产高性能分离膜，同时增强了对环境应用中PA膜结构-性能关系的理解。
{"title":"Engineering polyamide network topology via competitive interfacial polymerization for superior water permeance and ion selectivity","authors":"Xuewu Zhu , Feiyue Ge , Liping Qiu , Hong Peng , Fanduo Meng , Langming Bai , Feiyong Chen , Daliang Xu , Daoji Wu , Bin Liu","doi":"10.1016/j.memsci.2025.125107","DOIUrl":"10.1016/j.memsci.2025.125107","url":null,"abstract":"<div><div>Nanofiltration (NF) plays a critical role in advanced water treatment; however, the performance of conventional polyamide (PA) membranes is fundamentally limited by the permeance–selectivity trade-off, a consequence of the densely cross-linked network formed via trimesoyl chloride (TMC) and piperazine (PIP) reaction. To address this issue, this study presents a molecular-level engineering approach that redesigns the PA network architecture by employing a competitive interfacial polymerization (IP) process using mixed acyl chloride monomers. Specifically, isophthaloyl chloride (IPC) is introduced as a crosslinking modulator that competitively restrains the over-crosslinking of TMC and acts as a chain extender to enhance the flexibility of the polymer matrix. Density functional theory (DFT) calculations revealed that the distinct electrostatic potential differences among monomers drive this precise regulation, resulting in a hybrid network with optimized fractional free volume. This rationally tailored structure led to a significant improvement in membrane performance, exhibiting a high pure water permeance of 18.9 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> (2.5 times that of the pristine PA-TMC membrane) without compromising selectivity. Furthermore, the engineered membrane featured a highly electronegative and carboxyl-rich surface, which strengthens membrane–ion interactions via a synergistic surface complexation–charge shielding mechanism, thereby creating elevated ion transport barriers and enabling superior divalent ion separation (e.g., 82.9 % for MgCl<sub>2</sub> and >99.0 % for Na<sub>2</sub>SO<sub>4</sub>). Efficient removal of both natural organic matter and persistent negatively charged contaminants was achieved, with rejection rates exceeding 95 % for PFOA and reaching 99.5 % for large-molecule PFAS (e.g., PFODA). This study introduces a method to control polymer network formation using competitive reaction kinetics, yielding high-performance separation membranes while enhancing the understanding of the structure-property relationships in PA films for environmental applications.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125107"},"PeriodicalIF":9.0,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.memsci.2025.125093
Ajing Ding , Xing Fang , Jiaming Fei , Jingtao You , Quanhui Zhou , Fanghua Li , Yuting Zhang , Xuerui Wang , Lian Zhang , Qiaoqiao Zhou , Xuehong Gu
Clean syngas is valuable for fuel cells and high-value fuels/chemical synthesis; however, tar and particulate matter (PM) in syngas hinder its utilization. This study systematically investigated the steam gasification of six typical biowastes (covering agricultural, forestry, and aquatic categories) in an activated biochar catalyst-integrated SiC membrane reactor at 800 °C, focusing on the tar and PM formation and control mechanism. In control tests (without membrane, catalyst or steam), microalgae (MA) had the highest syngas tar content (395.6 g/m3), while herb residue (HR) showed the lowest (82.9 g/m3). MA also had the highest PM content (9.1 g/m3), followed by walnut shell (WS, 7.0 g/m3), whereas corncob (CC) and poplar wood (PW) had the lowest (1.2–1.4 g/m3), with PM content dependent more on coke from volatile polymerization than feedstock ash. In the catalyst-integrated membrane reactor, steam gasification of biowastes achieved tar conversion efficiencies of 88 %–96 % and PM removal efficiencies of 94 %–99 % across all biowastes, with excellent stability over 400 min. This performance should be attributed to the synergies among the three core components: the SiC membrane retained coarse PM to protect catalyst active sites; steam suppressed carbon deposition on both membrane and catalyst via coke reforming; and the biochar catalyst promoted tar cracking/reforming, followed by steam and then the membrane. These findings highlight the unique complementary roles of the integrated system, emphasizing the need to tailor gasification processes to biowaste characteristics for efficient clean syngas production.
{"title":"Synergistic control of tar and particulate matter in steam gasification of six typical biowastes using a catalyst-integrated SiC membrane reactor","authors":"Ajing Ding , Xing Fang , Jiaming Fei , Jingtao You , Quanhui Zhou , Fanghua Li , Yuting Zhang , Xuerui Wang , Lian Zhang , Qiaoqiao Zhou , Xuehong Gu","doi":"10.1016/j.memsci.2025.125093","DOIUrl":"10.1016/j.memsci.2025.125093","url":null,"abstract":"<div><div>Clean syngas is valuable for fuel cells and high-value fuels/chemical synthesis; however, tar and particulate matter (PM) in syngas hinder its utilization. This study systematically investigated the steam gasification of six typical biowastes (covering agricultural, forestry, and aquatic categories) in an activated biochar catalyst-integrated SiC membrane reactor at 800 °C, focusing on the tar and PM formation and control mechanism. In control tests (without membrane, catalyst or steam), microalgae (MA) had the highest syngas tar content (395.6 g/m<sup>3</sup>), while herb residue (HR) showed the lowest (82.9 g/m<sup>3</sup>). MA also had the highest PM content (9.1 g/m<sup>3</sup>), followed by walnut shell (WS, 7.0 g/m<sup>3</sup>), whereas corncob (CC) and poplar wood (PW) had the lowest (1.2–1.4 g/m<sup>3</sup>), with PM content dependent more on coke from volatile polymerization than feedstock ash. In the catalyst-integrated membrane reactor, steam gasification of biowastes achieved tar conversion efficiencies of 88 %–96 % and PM removal efficiencies of 94 %–99 % across all biowastes, with excellent stability over 400 min. This performance should be attributed to the synergies among the three core components: the SiC membrane retained coarse PM to protect catalyst active sites; steam suppressed carbon deposition on both membrane and catalyst via coke reforming; and the biochar catalyst promoted tar cracking/reforming, followed by steam and then the membrane. These findings highlight the unique complementary roles of the integrated system, emphasizing the need to tailor gasification processes to biowaste characteristics for efficient clean syngas production.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125093"},"PeriodicalIF":9.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.memsci.2025.125095
Zezhou Zhang , Yinghe Ma , Caini Liu , Boyu Zhao , Ao Shen , Meiqi Ye , Zhongqi Li , Wenyi Wang
Nanofiltration (NF) membranes are critical for sustainable water purification, yet the trade-off between water permeability and ion selectivity, coupled with limited monovalent ion rejection and fouling susceptibility, remains unresolved. In this study, we report a “novel multi-functional strategy” to fabricate alkalinity-modified MXene (Alk-MXene) NF membranes via interfacial polymerization, integrating three synergistic design features rarely combined in prior work: (1) Alk-MXene-induced formation of Turing-like microstructures, (2) electro-assisted separation for enhanced monovalent ion rejection, and (3) robust anti-fouling/hydrophilic properties derived from Alk-MXene's surface chemistry. Alk-MXene was dispersed in the aqueous phase to polymerize with trimesoyl chloride on a polyethersulfone support. The Turing-like structures—driven by reaction-diffusion during polymerization—created well-defined microporous water channels, resolving the permeability-selectivity trade-off. The optimized membrane achieved a water flux of 21.01 L m−2 h−1·bar−1, with high rejection rates for divalent salts (98.73 % MgSO4, 98.17 % Na2SO4, 95.21 % MgCl2) and improved monovalent salt rejection (40.38 % NaCl) via the Donnan effect. Notably, applying a 4 V external electric field further enhanced NaCl rejection by 15 % (to 57.38 %) through electrokinetic transport—a key advance for treating low-salinity wastewater where monovalent ion control is critical. Long-term stability tests (420 min) showed >87 % flux retention, while anti-fouling assessments revealed a flux recovery rate (FRR) of >83 % after BSA fouling (rising to 90 % with electro-cleaning), attributed to Alk-MXene's hydrophilicity and negative surface charge. These findings highlight the promising potential of Alk-MXene NF membranes for sustainable, energy-efficient water purification, providing an optimal combination of high permeability, selectivity, and durability for next-generation desalination and wastewater treatment technologies.
{"title":"Alkalinity-modified MXene nanofiltration membranes combining turing-like structures and electro-assisted separation","authors":"Zezhou Zhang , Yinghe Ma , Caini Liu , Boyu Zhao , Ao Shen , Meiqi Ye , Zhongqi Li , Wenyi Wang","doi":"10.1016/j.memsci.2025.125095","DOIUrl":"10.1016/j.memsci.2025.125095","url":null,"abstract":"<div><div>Nanofiltration (NF) membranes are critical for sustainable water purification, yet the trade-off between water permeability and ion selectivity, coupled with limited monovalent ion rejection and fouling susceptibility, remains unresolved. In this study, we report a “novel multi-functional strategy” to fabricate alkalinity-modified MXene (Alk-MXene) NF membranes via interfacial polymerization, integrating three synergistic design features rarely combined in prior work: (1) Alk-MXene-induced formation of Turing-like microstructures, (2) electro-assisted separation for enhanced monovalent ion rejection, and (3) robust anti-fouling/hydrophilic properties derived from Alk-MXene's surface chemistry. Alk-MXene was dispersed in the aqueous phase to polymerize with trimesoyl chloride on a polyethersulfone support. The Turing-like structures—driven by reaction-diffusion during polymerization—created well-defined microporous water channels, resolving the permeability-selectivity trade-off. The optimized membrane achieved a water flux of 21.01 L m<sup>−2</sup> h<sup>−1</sup>·bar<sup>−1</sup>, with high rejection rates for divalent salts (98.73 % MgSO<sub>4</sub>, 98.17 % Na<sub>2</sub>SO<sub>4</sub>, 95.21 % MgCl<sub>2</sub>) and improved monovalent salt rejection (40.38 % NaCl) via the Donnan effect. Notably, applying a 4 V external electric field further enhanced NaCl rejection by 15 % (to 57.38 %) through electrokinetic transport—a key advance for treating low-salinity wastewater where monovalent ion control is critical. Long-term stability tests (420 min) showed >87 % flux retention, while anti-fouling assessments revealed a flux recovery rate (FRR) of >83 % after BSA fouling (rising to 90 % with electro-cleaning), attributed to Alk-MXene's hydrophilicity and negative surface charge. These findings highlight the promising potential of Alk-MXene NF membranes for sustainable, energy-efficient water purification, providing an optimal combination of high permeability, selectivity, and durability for next-generation desalination and wastewater treatment technologies.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125095"},"PeriodicalIF":9.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.memsci.2025.125103
Xin Ji , Ming Chen , DongLu Fang , Yujin Lin , Xiaodong Li , Wei-xian Zhang , Zilong Deng
Methylene blue (MB), typically regarded as a model dye pollutant, was repurposed as a multifunctional component to enhance the performance of metal-organic framework/cellulose nanofiber (MIL@CNF) membranes. By immobilizing MB into MIL, MB-MIL@CNF membranes were developed that integrated photosensitization, catalytic activity, and antifouling capability. The optimized MB-MIL@CNF membrane exhibited markedly enhanced water flux and achieved 93.71 % levofloxacin (LEVO) degradation under visible light irradiation, surpassing pristine MIL@CNF (59.95 %). Mechanistic studies revealed that MB acted as a photosensitizer and electronic modulator, broadening light absorption, facilitating charge transfer, and generating 1O2 and ·O2− for efficient LEVO degradation. In addition, MB incorporation significantly improved antifouling performance through light-driven self-cleaning. Stability tests confirmed the strong adsorption of MB by MIL, without detectable leaching or secondary toxicity. Phytotoxicity assays further demonstrated that MB-MIL@CNF membranes not only eliminated LEVO-induced growth inhibition but also posed minimal ecological risk. This work transformed a conventional dye pollutant into a functional sensitizer, providing new insights into the synergistic design of sustainable, high-performance catalytic membranes for water purification.
{"title":"Beyond a pollutant: multifunctional methylene blue drives hydrophilicity, catalysis, and antifouling in filtration membranes","authors":"Xin Ji , Ming Chen , DongLu Fang , Yujin Lin , Xiaodong Li , Wei-xian Zhang , Zilong Deng","doi":"10.1016/j.memsci.2025.125103","DOIUrl":"10.1016/j.memsci.2025.125103","url":null,"abstract":"<div><div>Methylene blue (MB), typically regarded as a model dye pollutant, was repurposed as a multifunctional component to enhance the performance of metal-organic framework/cellulose nanofiber (MIL@CNF) membranes. By immobilizing MB into MIL, MB-MIL@CNF membranes were developed that integrated photosensitization, catalytic activity, and antifouling capability. The optimized MB-MIL@CNF membrane exhibited markedly enhanced water flux and achieved 93.71 % levofloxacin (LEVO) degradation under visible light irradiation, surpassing pristine MIL@CNF (59.95 %). Mechanistic studies revealed that MB acted as a photosensitizer and electronic modulator, broadening light absorption, facilitating charge transfer, and generating <sup>1</sup>O<sub>2</sub> and ·O<sub>2</sub><sup>−</sup> for efficient LEVO degradation. In addition, MB incorporation significantly improved antifouling performance through light-driven self-cleaning. Stability tests confirmed the strong adsorption of MB by MIL, without detectable leaching or secondary toxicity. Phytotoxicity assays further demonstrated that MB-MIL@CNF membranes not only eliminated LEVO-induced growth inhibition but also posed minimal ecological risk. This work transformed a conventional dye pollutant into a functional sensitizer, providing new insights into the synergistic design of sustainable, high-performance catalytic membranes for water purification.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125103"},"PeriodicalIF":9.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.memsci.2025.125105
Taotao Gao , Jiating Liu , Fusheng Pan , Xingchun Li , Hongju Da , Ming Xue , Xiangyu Cui , Han Zhang , Jian Lu , Zhongyi Jiang
Volatile organic compounds (VOCs) are pollutants detrimental to human health and the environment, necessitating the development of efficient separation technologies to support sustainable societal progress. Hybrid membranes incorporating metalated covalent organic frameworks (MCOFs) have shown great potential for VOCs separation due to the synergistic combination of polymer processability and the selective adsorption capacity of MCOFs. However, the performance of conventional MCOFs is limited by their microporous structures, which restrict molecular diffusion and accessibility to metal active sites. Herein, we have designed a mesoporous Cu(I)-metalated COF (Cu3L3-BD) with a pore diameter of 3.8 nm, which was further incorporated into poly(ether-block-amide) (Pebax) matrix to fabricate hybrid membranes (Pebax-Cu3L3-BD) for VOCs separation. The mesoporous channels facilitate improved gas transport and maximize exposure of Cu(I) coordination sites, thus enhancing the dissolution-diffusion process and improving the selectivity of Pebax-Cu3L3-BD. With a filler loading of 3 wt%, the Pebax-Cu3L3-BD exhibited optimal toluene permeance of 1.67 × 10−6 mol μm m−2 s−1 Pa−1 and selectivity of 730, with the stability maintained over 120 h.
{"title":"Mesoporous metalated covalent organic framework hybrid membrane for efficient VOCs separation","authors":"Taotao Gao , Jiating Liu , Fusheng Pan , Xingchun Li , Hongju Da , Ming Xue , Xiangyu Cui , Han Zhang , Jian Lu , Zhongyi Jiang","doi":"10.1016/j.memsci.2025.125105","DOIUrl":"10.1016/j.memsci.2025.125105","url":null,"abstract":"<div><div>Volatile organic compounds (VOCs) are pollutants detrimental to human health and the environment, necessitating the development of efficient separation technologies to support sustainable societal progress. Hybrid membranes incorporating metalated covalent organic frameworks (MCOFs) have shown great potential for VOCs separation due to the synergistic combination of polymer processability and the selective adsorption capacity of MCOFs. However, the performance of conventional MCOFs is limited by their microporous structures, which restrict molecular diffusion and accessibility to metal active sites. Herein, we have designed a mesoporous Cu(I)-metalated COF (Cu<sub>3</sub>L<sub>3</sub>-BD) with a pore diameter of 3.8 nm, which was further incorporated into poly(ether-block-amide) (Pebax) matrix to fabricate hybrid membranes (Pebax-Cu<sub>3</sub>L<sub>3</sub>-BD) for VOCs separation. The mesoporous channels facilitate improved gas transport and maximize exposure of Cu(I) coordination sites, thus enhancing the dissolution-diffusion process and improving the selectivity of Pebax-Cu<sub>3</sub>L<sub>3</sub>-BD. With a filler loading of 3 wt%, the Pebax-Cu<sub>3</sub>L<sub>3</sub>-BD exhibited optimal toluene permeance of 1.67 × 10<sup>−6</sup> mol μm m<sup>−2</sup> s<sup>−1</sup> Pa<sup>−1</sup> and selectivity of 730, with the stability maintained over 120 h.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125105"},"PeriodicalIF":9.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-26DOI: 10.1016/j.memsci.2025.125099
Huiping Zhang , Yuchen Zhao , Lingfeng Dai , Tianshun Xu , Kaiyun Fu , Xianfu Chen , Minghui Qiu , Peng Xu , Yiqun Fan
Direct air capture (DAC) is constrained by the inherently low driving force for CO2 capture. To address this challenge, this study employs multi-channel ceramic membrane contactors as the highly efficient gas-liquid contacting device. Here, we systematically investigated the performance of 19,37,61-channel membrane configurations through a combination of experiment and computational fluid dynamics (CFD) analysis. Among the tested configurations, the 37-channel membrane exhibited superior DAC performance, attributed to its balanced flow distribution and optimal gas-liquid contact characteristics. And it achieved a stable capture performance with a CO2 absorption flux of 0.06 mol m−2 h−1. Further experiments demonstrated that the scaled-up module was able to operate continuously for 170 h with stable performance and ∼2.2 kg CO2 captured from ambient air. These results underscore the scalability and practical viability of multi-channel membrane contactors for modular DAC systems.
{"title":"Analysis of multi-channel membrane contactor with high packing density for direct air capture","authors":"Huiping Zhang , Yuchen Zhao , Lingfeng Dai , Tianshun Xu , Kaiyun Fu , Xianfu Chen , Minghui Qiu , Peng Xu , Yiqun Fan","doi":"10.1016/j.memsci.2025.125099","DOIUrl":"10.1016/j.memsci.2025.125099","url":null,"abstract":"<div><div>Direct air capture (DAC) is constrained by the inherently low driving force for CO<sub>2</sub> capture. To address this challenge, this study employs multi-channel ceramic membrane contactors as the highly efficient gas-liquid contacting device. Here, we systematically investigated the performance of 19,37,61-channel membrane configurations through a combination of experiment and computational fluid dynamics (CFD) analysis. Among the tested configurations, the 37-channel membrane exhibited superior DAC performance, attributed to its balanced flow distribution and optimal gas-liquid contact characteristics. And it achieved a stable capture performance with a CO<sub>2</sub> absorption flux of 0.06 mol m<sup>−2</sup> h<sup>−1</sup>. Further experiments demonstrated that the scaled-up module was able to operate continuously for 170 h with stable performance and ∼2.2 kg CO<sub>2</sub> captured from ambient air. These results underscore the scalability and practical viability of multi-channel membrane contactors for modular DAC systems.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"741 ","pages":"Article 125099"},"PeriodicalIF":9.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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