Pub Date : 2026-04-01Epub Date: 2026-02-05DOI: 10.1016/j.memsci.2026.125244
Zhengqing Zhang , Min Wang , Wenjing Tian , Xiaohao Cao , Mengdi Zhao , Yuxiu Sun , Zhihua Qiao
C3H8-selective membranes are vital for efficient C3H6/C3H8 separation, yet the rational design of high-performance MOF-based membranes remains challenging. In this study, the CoRE MOFs satisfying key geometric criteria were initially screened, and their separation performance and underlying mechanisms were evaluated via high-throughput computational screening (HTCS). The obtained features and separation performance were subsequently used to develop machine learning (ML) models. Guided by top-performing ML models (CatBoost and Random Forest), key descriptors were identified to enable the rational design of MOF-based membranes. Accordingly, a total of 8338 IL@MOF structures were constructed via configurational-bias Monte Carlo simulations, of which ∼65.3% (5447) were structurally feasible and screened for performance evaluation. The membrane performance score (MPS) of 29 IL@MOF composite membranes exceeded that of the top-performing CoRE MOF (FUYCIN), with the best-performing composite membrane, [BMIM][BF4]@UMODEH14, exhibiting a 4.7-fold higher performance than FUYCIN. This ML-driven hierarchical strategy enables data-informed design and screening of MOF-based membranes, providing a generalizable framework for the accelerated discovery of next-generation membranes for challenging gas separations.
{"title":"Machine learning-enabled design of MOF-based membranes for efficient C3H8-selective separation","authors":"Zhengqing Zhang , Min Wang , Wenjing Tian , Xiaohao Cao , Mengdi Zhao , Yuxiu Sun , Zhihua Qiao","doi":"10.1016/j.memsci.2026.125244","DOIUrl":"10.1016/j.memsci.2026.125244","url":null,"abstract":"<div><div>C<sub>3</sub>H<sub>8</sub>-selective membranes are vital for efficient C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation, yet the rational design of high-performance MOF-based membranes remains challenging. In this study, the CoRE MOFs satisfying key geometric criteria were initially screened, and their separation performance and underlying mechanisms were evaluated via high-throughput computational screening (HTCS). The obtained features and separation performance were subsequently used to develop machine learning (ML) models. Guided by top-performing ML models (CatBoost and Random Forest), key descriptors were identified to enable the rational design of MOF-based membranes. Accordingly, a total of 8338 IL@MOF structures were constructed via configurational-bias Monte Carlo simulations, of which ∼65.3% (5447) were structurally feasible and screened for performance evaluation. The membrane performance score (MPS) of 29 IL@MOF composite membranes exceeded that of the top-performing CoRE MOF (FUYCIN), with the best-performing composite membrane, [BMIM][BF<sub>4</sub>]@UMODEH14, exhibiting a 4.7-fold higher performance than FUYCIN. This ML-driven hierarchical strategy enables data-informed design and screening of MOF-based membranes, providing a generalizable framework for the accelerated discovery of next-generation membranes for challenging gas separations.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"745 ","pages":"Article 125244"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172334","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}
Poly(lactic acid) (PLA) is a biomass-derived biodegradable polymer that shows promise as a circular resource for water-treatment membranes. The molecular structure of PLA affects its phase separation behavior, enabling control of pore formation to improve membrane performance. Changing the molecular chain density of PLA also affects its biodegradation behavior. However, conventional polymerization methods hardly provide PLA with both narrow molecular-weight distribution and high molecular weight, which limits research on the molecular structure of PLA. In this study, linear and star-branched PLA with four or eight arms were synthesized via organocatalyzed ring-opening polymerization, achieving a weight-average molecular weight (Mw) of ∼95,000 and narrow dispersity (≤1.2). PLA membranes were prepared via nonsolvent-induced phase separation and the effects of branch number and Mw on pore structure and hydrolysis behavior were investigated. The membrane surfaces exhibited fine pores with underlying finger-like macrovoids. Molecular weight cut-off increased with branch number (linear: 15,000 Da; four: 17,000 Da; eight: 52,000 Da). This trend was attributed to the decrease in solution viscosity with increasing branch number, which facilitated phase separation and pore growth. The decrease rate of molecular weight in accelerated hydrolysis tests (pH 9, 65 °C, 215 h) was 90 % for four-arm PLA, 70 % for linear, and 49 % for eight-arm PLA. A moderate PLA branching structure promoted hydrolysis, whereas an excessive branch number increased the chain density near the branch points, inhibiting water penetration and hydrolysis. These findings indicate that branch number, Mw, and viscosity control are important for improving membrane performance and degradability.
聚乳酸（PLA）是一种生物质衍生的可生物降解聚合物，有望成为水处理膜的循环资源。聚乳酸的分子结构影响其相分离行为，从而控制孔隙形成以提高膜性能。改变聚乳酸的分子链密度也会影响其生物降解行为。然而，传统的聚合方法很难同时提供PLA窄分子量分布和高分子量，这限制了对PLA分子结构的研究。在这项研究中，通过有机催化开环聚合，合成了具有四臂或八臂的线性和星形支链PLA，获得了平均分子量（Mw）约95,000和窄分散度（≤1.2）。采用非溶剂诱导相分离法制备了聚乳酸膜，考察了支链数和分子量对膜孔结构和水解行为的影响。膜表面有细孔，下有指状大孔。分子量临界值随着分支数的增加而增加（线性：15,000 Da; 4: 17,000 Da; 8: 52,000 Da）。这一趋势是由于随着支链数的增加，溶液粘度降低，有利于相分离和孔隙的生长。在加速水解试验（pH为9,65°C, 215 h）中，四臂PLA的分子量降低率为90%，线性PLA为70%，八臂PLA为49%。适度的聚乳酸支链结构促进了水解，过多的支链数量增加了分支点附近的链密度，抑制了水的渗透和水解。这些结果表明，支链数、分子量和粘度控制对提高膜的性能和降解性很重要。
{"title":"Effect of molecular structure on porous structure and performance of star-branched poly(lactic acid) ultrafiltration membranes","authors":"Koichi Takada , Akinori Okada , Hiroshi Hirano , Joji Kadota , Tooru Kitagawa , Hideto Matsuyama , Tomohisa Yoshioka , Keizo Nakagawa","doi":"10.1016/j.memsci.2026.125225","DOIUrl":"10.1016/j.memsci.2026.125225","url":null,"abstract":"<div><div>Poly(lactic acid) (PLA) is a biomass-derived biodegradable polymer that shows promise as a circular resource for water-treatment membranes. The molecular structure of PLA affects its phase separation behavior, enabling control of pore formation to improve membrane performance. Changing the molecular chain density of PLA also affects its biodegradation behavior. However, conventional polymerization methods hardly provide PLA with both narrow molecular-weight distribution and high molecular weight, which limits research on the molecular structure of PLA. In this study, linear and star-branched PLA with four or eight arms were synthesized via organocatalyzed ring-opening polymerization, achieving a weight-average molecular weight (<em>M</em><sub>w</sub>) of ∼95,000 and narrow dispersity (≤1.2). PLA membranes were prepared via nonsolvent-induced phase separation and the effects of branch number and <em>M</em><sub>w</sub> on pore structure and hydrolysis behavior were investigated. The membrane surfaces exhibited fine pores with underlying finger-like macrovoids. Molecular weight cut-off increased with branch number (linear: 15,000 Da; four: 17,000 Da; eight: 52,000 Da). This trend was attributed to the decrease in solution viscosity with increasing branch number, which facilitated phase separation and pore growth. The decrease rate of molecular weight in accelerated hydrolysis tests (pH 9, 65 °C, 215 h) was 90 % for four-arm PLA, 70 % for linear, and 49 % for eight-arm PLA. A moderate PLA branching structure promoted hydrolysis, whereas an excessive branch number increased the chain density near the branch points, inhibiting water penetration and hydrolysis. These findings indicate that branch number, <em>M</em><sub>w</sub>, and viscosity control are important for improving membrane performance and degradability.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"744 ","pages":"Article 125225"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185556","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 : 2026-04-01Epub Date: 2026-02-02DOI: 10.1016/j.memsci.2026.125232
Yuyang Wang , Yeernaer Arixin , Dandan Liu , Hu Yang
Dye wastewater poses serious environmental risks because of its high ecotoxicity; however, conventional flocculation and ultrafiltration often suffer from limited dye removal efficiency and severe membrane fouling. This study simply synthesized a novel starch-based flocculant (CS-ECH) with cationically branched structure by slight crosslinking of a linear cationic starch (CS) with epichlorohydrin. CS-ECH, as ultrafiltration pretreatment, was applied to remove acid green 25 (AG25) in water, a typical synthetic dye. Compared with polyaluminum chloride and its linear precursor, the optimized CS-ECH showed superior flocculation efficiency including a wide effective dosage range (30.0–80.0 mg/L) and a high removal rate (99.24%). Its cationically branched structure bears a loose network conformation, enhancing bridging and sweeping effects, promoting the formation of large but loose flocs and thus high dye removal efficiency, in addition to efficient charge neutralization. The calculated interaction energy and coordination number from molecular dynamics simulations revealed CS-ECH had stronger interactions with and also captured more AG25 than CS due to the distinct structure of CS-ECH. The following ultrafiltration achieved a complete decolorization, minimized the flux decline with a steady-state normalized flux of 0.62, and mitigated reversible and irreversible fouling by 34.2% and 85.3% respectively, owing to the previous formation of a porous, easily detachable cake layer by CS-ECH. The flocculation-ultrafiltration combination also exhibited excellent membrane reusability and adaptability to various simulated dye wastewaters and an actual dye effluent. Overall, CS-ECH is a low-cost, environmentally-friendly, and efficient flocculant with notable application potentials in flocculation–ultrafiltration integrated systems for advanced dye wastewater treatment.
{"title":"Cationically branched starch-based flocculants for synergistic flocculation-ultrafiltration treatment of dye wastewaters: Performance enhancement and efficient membrane fouling mitigation","authors":"Yuyang Wang , Yeernaer Arixin , Dandan Liu , Hu Yang","doi":"10.1016/j.memsci.2026.125232","DOIUrl":"10.1016/j.memsci.2026.125232","url":null,"abstract":"<div><div>Dye wastewater poses serious environmental risks because of its high ecotoxicity; however, conventional flocculation and ultrafiltration often suffer from limited dye removal efficiency and severe membrane fouling. This study simply synthesized a novel starch-based flocculant (CS-ECH) with cationically branched structure by slight crosslinking of a linear cationic starch (CS) with epichlorohydrin. CS-ECH, as ultrafiltration pretreatment, was applied to remove acid green 25 (AG25) in water, a typical synthetic dye. Compared with polyaluminum chloride and its linear precursor, the optimized CS-ECH showed superior flocculation efficiency including a wide effective dosage range (30.0–80.0 mg/L) and a high removal rate (99.24%). Its cationically branched structure bears a loose network conformation, enhancing bridging and sweeping effects, promoting the formation of large but loose flocs and thus high dye removal efficiency, in addition to efficient charge neutralization. The calculated interaction energy and coordination number from molecular dynamics simulations revealed CS-ECH had stronger interactions with and also captured more AG25 than CS due to the distinct structure of CS-ECH. The following ultrafiltration achieved a complete decolorization, minimized the flux decline with a steady-state normalized flux of 0.62, and mitigated reversible and irreversible fouling by 34.2% and 85.3% respectively, owing to the previous formation of a porous, easily detachable cake layer by CS-ECH. The flocculation-ultrafiltration combination also exhibited excellent membrane reusability and adaptability to various simulated dye wastewaters and an actual dye effluent. Overall, CS-ECH is a low-cost, environmentally-friendly, and efficient flocculant with notable application potentials in flocculation–ultrafiltration integrated systems for advanced dye wastewater treatment.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"745 ","pages":"Article 125232"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116636","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 : 2026-04-01Epub Date: 2026-02-01DOI: 10.1016/j.memsci.2026.125212
Genyu Wei , Jiejun Zeng , Xiaoyu Li , Yunji Xie , Di Liu , Jiaran Song , Yuanlong Wu , Haidong Ma , Le Wang , Zhe Wang
Commercial perfluoro sulfonic acid membranes (e.g., Nafion) are limited by high cost, strong humidity dependence, and excessive methanol crossover in direct methanol fuel cells (DMFCs). Herein, a series of semi-crystalline sulfonated poly (aromatic ether ketone sulfone) (SPPESK-x) membranes is synthesized through nucleophilic polycondensation followed by post-sulfonation. By incorporating densely sulfonated side chains and a crystalline hydrophobic backbone, these membranes achieve an excellent balance between proton conductivity and dimensional stability. The optimized membrane (SPPESK-12.5) exhibits an ultra-low in-plane swelling ratio of 16.5% at 80 °C, owing to its semi-crystalline structure, while delivering a high proton conductivity of 0.184 S cm−1 under the same conditions. Furthermore, it shows significantly reduced methanol permeability and superior selectivity compared with control membranes. Fuel-cell tests using concentrated methanol (10 M) and under unpressurized H2/O2 and H2/air conditions demonstrate promising power outputs and stable operation over 100 h. This work provides a viable strategy for designing high-performance hydrocarbon-based proton exchange membranes that combine enhanced proton conductivity with robust mechanical stability under demanding operating conditions.
商用全氟磺酸膜（例如，Nafion）受到成本高、湿度依赖性强以及直接甲醇燃料电池（dmfc）中甲醇交叉过多的限制。本文通过亲核缩聚和后磺化合成了一系列半结晶磺化聚芳醚酮砜（SPPESK-x）膜。通过结合密集的磺化侧链和结晶疏水主链，这些膜在质子导电性和尺寸稳定性之间取得了良好的平衡。优化后的膜（SPPESK-12.5）由于其半晶体结构，在80°C时具有16.5%的超低面内膨胀率，同时在相同条件下具有0.184 S cm−1的高质子电导率。此外，与对照膜相比，它具有显著降低甲醇渗透率和优越的选择性。燃料电池在浓缩甲醇（10 M）和非加压H2/O2和H2/空气条件下的测试表明，有希望的功率输出和超过100小时的稳定运行。这项工作为设计高性能碳氢化合物质子交换膜提供了可行的策略，该膜在苛刻的操作条件下结合了增强的质子导电性和强大的机械稳定性。
{"title":"Engineering balanced high-conductivity and low-swelling semi-crystalline sulfonated poly (aromatic ether ketone sulfone) proton exchange membranes for fuel cells","authors":"Genyu Wei , Jiejun Zeng , Xiaoyu Li , Yunji Xie , Di Liu , Jiaran Song , Yuanlong Wu , Haidong Ma , Le Wang , Zhe Wang","doi":"10.1016/j.memsci.2026.125212","DOIUrl":"10.1016/j.memsci.2026.125212","url":null,"abstract":"<div><div>Commercial perfluoro sulfonic acid membranes (e.g., Nafion) are limited by high cost, strong humidity dependence, and excessive methanol crossover in direct methanol fuel cells (DMFCs). Herein, a series of semi-crystalline sulfonated poly (aromatic ether ketone sulfone) (SPPESK-x) membranes is synthesized through nucleophilic polycondensation followed by post-sulfonation. By incorporating densely sulfonated side chains and a crystalline hydrophobic backbone, these membranes achieve an excellent balance between proton conductivity and dimensional stability. The optimized membrane (SPPESK-12.5) exhibits an ultra-low in-plane swelling ratio of 16.5% at 80 °C, owing to its semi-crystalline structure, while delivering a high proton conductivity of 0.184 S cm<sup>−1</sup> under the same conditions. Furthermore, it shows significantly reduced methanol permeability and superior selectivity compared with control membranes. Fuel-cell tests using concentrated methanol (10 M) and under unpressurized H<sub>2</sub>/O<sub>2</sub> and H<sub>2</sub>/air conditions demonstrate promising power outputs and stable operation over 100 h. This work provides a viable strategy for designing high-performance hydrocarbon-based proton exchange membranes that combine enhanced proton conductivity with robust mechanical stability under demanding operating conditions.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"744 ","pages":"Article 125212"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185501","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 : 2026-04-01Epub Date: 2026-01-30DOI: 10.1016/j.memsci.2026.125229
Jiangnan Wang , Long Li , Yu Jiang , Jinli Zhang , Xueqin Li
In this study, SCDs@MOF was synthesized by combining sulfonated carbon quantum dots (SCDs) with MOF-808, and it was incorporated into sulfonated poly (ether ether ketone) (SPEEK) matrix to fabricate mixed matrix membranes (MMMs) for efficient CO2 separation. Thereinto, SCDs with negative charges and MOF-808 with positive charges in SCDs@MOF can play synergistic roles in MMMs. The built-in electric field (BIEF) can be formed due to the opposite charges of SCDs and MOF-808, and it can provide driving force to promoting the formation of anion (HCO3−) and cation (H+) from CO2 and H2O. In addition, the interconnected anion-cation transport pathways in SCDs@MOF can be constructed in MMMs, and they allowed HCO3− and H+ to be rapidly transported, attributing to the directional driving of charged ions by BIEF. As a result, the construction of the anion-cation transport pathways can improve CO2 separation performance of MMMs. Therefore, SPEEK/SCDs@MOF MMMs were endowed with the excellent CO2 separation performance. And the optimum CO2 permeability and CO2/CH4 selectivity reached 1716 ± 48 Barrer and 29 ± 1.1, respectively, approaching 2019 upper bound. It implied that the formation of anion-cation transport pathways by BIEF in MMMs was a potential strategy for efficient CO2 separation.
{"title":"Constructing anion-cation transport pathways by built-in electric fields in membranes for efficient CO2 separation","authors":"Jiangnan Wang , Long Li , Yu Jiang , Jinli Zhang , Xueqin Li","doi":"10.1016/j.memsci.2026.125229","DOIUrl":"10.1016/j.memsci.2026.125229","url":null,"abstract":"<div><div>In this study, SCDs@MOF was synthesized by combining sulfonated carbon quantum dots (SCDs) with MOF-808, and it was incorporated into sulfonated poly (ether ether ketone) (SPEEK) matrix to fabricate mixed matrix membranes (MMMs) for efficient CO<sub>2</sub> separation. Thereinto, SCDs with negative charges and MOF-808 with positive charges in SCDs@MOF can play synergistic roles in MMMs. The built-in electric field (BIEF) can be formed due to the opposite charges of SCDs and MOF-808, and it can provide driving force to promoting the formation of anion (HCO<sub>3</sub><sup>−</sup>) and cation (H<sup>+</sup>) from CO<sub>2</sub> and H<sub>2</sub>O. In addition, the interconnected anion-cation transport pathways in SCDs@MOF can be constructed in MMMs, and they allowed HCO<sub>3</sub><sup>−</sup> and H<sup>+</sup> to be rapidly transported, attributing to the directional driving of charged ions by BIEF. As a result, the construction of the anion-cation transport pathways can improve CO<sub>2</sub> separation performance of MMMs. Therefore, SPEEK/SCDs@MOF MMMs were endowed with the excellent CO<sub>2</sub> separation performance. And the optimum CO<sub>2</sub> permeability and CO<sub>2</sub>/CH<sub>4</sub> selectivity reached 1716 ± 48 Barrer and 29 ± 1.1, respectively, approaching 2019 upper bound. It implied that the formation of anion-cation transport pathways by BIEF in MMMs was a potential strategy for efficient CO<sub>2</sub> separation.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"744 ","pages":"Article 125229"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185555","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 : 2026-04-01Epub Date: 2026-01-23DOI: 10.1016/j.memsci.2026.125205
Soumitra Panda , Bholanath Mahanty , Debasis Sen , Satish Mandal , Pramilla D. Sawant , Arunasis Bhattacharyya
Generally, aggregation and synergism are common phenomenon in solvent extraction process when two amphiphilic extractants, one acidic and another neutral were employed for the metal ion extraction. Again, aggregation may drive the synergistic extraction of metal ions in a multi extractant system. However, to the best of our knowledge, the correlation between aggregation and synergism is unexplored in a more complex system like mixed extractant based polymeric plasticized membrane. Herein, we observed synergistic extraction of Am(III) from a dilute nitric acid solution (0.01–2 M) with a nitrophenyl octyl ether (NPOE) plasticized cellulose triacetate (CTA) based polymer inclusion membrane (PIM) containing an acidic extractant, di(2-ethylhexyl)phosphoric acid (D2EHPA) and a neutral extractant, N,N,N′,N′-tetraoctyldiglycolamide (TODGA). The Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), small angle X‐ray scattering (SAXS) and extraction studies indicate the involvement of both the ligand in the extraction of Eu(III) (considered as surrogate of Am(III)) and the evidence of aggregate formation in the structure of membrane. A possible mechanism was given to explain how aggregation synergistically assists in the extraction of metal ion based on the results from the SAXS studies. The self diffusion coefficients of Eu(III) was determined by non-stationary radiotracer diffusion method which nicely correlate with the size of the aggregate from SAXS studies of the membranes. The mixed membrane with a composition of D2EHPA and TODGA in the mole ratio of 2:1 follows the Langmuir isotherm model and pseudo second order kinetic model, both indicating a chemisorption process for the uptake of Eu(III) with a maximum uptake capacity of approximately 21 mg/g of PIM. The mixed membrane also employed for recovery of Am(III) from a filter paper waste sample which indicated ∼90 % recovery of the metal ion at 0.01 M HNO3 indicating possible application of the developed synergistic PIM in the analysis of real samples.
一般来说，两亲性萃取剂分别为酸性和中性萃取金属离子时，在溶剂萃取过程中会出现聚集和协同作用的现象。同样，在多萃取剂体系中，聚合可以驱动金属离子的协同萃取。然而，据我们所知，聚集和协同作用之间的关系尚未在更复杂的系统中探索，如混合萃取剂基聚合物增塑膜。在此，我们观察了在稀薄的硝酸溶液（0.01-2 M）中，硝基苯基辛醚（NPOE）增塑纤维素三乙酸酯（CTA）基聚合物包合膜（PIM）与酸性萃取剂二（2-乙基己基）磷酸（D2EHPA）和中性萃取剂N，N,N ',N ' -四辛基二乙醇酰胺（TODGA）协同萃取Am（III）。傅里叶变换红外光谱（FTIR）、光致发光（PL）、小角度X射线散射（SAXS）和萃取研究表明，配体参与了Eu(III)（被认为是Am（III）的替代品）的萃取，并在膜结构中形成聚集体。基于SAXS研究的结果，给出了一种可能的机制来解释聚集如何协同协助金属离子的提取。Eu（III）的自扩散系数由非稳态放射性示踪剂扩散法测定，该方法与膜的SAXS研究中聚集体的大小有很好的相关性。D2EHPA和TODGA摩尔比为2:1的混合膜符合Langmuir等温线模型和准二级动力学模型，表明其对Eu（III）的吸收是一个化学吸附过程，最大吸收能力约为21 mg/g PIM。该混合膜还用于从滤纸废样品中回收Am(III)，表明在0.01 M HNO3下金属离子回收率为~ 90%，表明所开发的协同PIM可能应用于实际样品的分析。
{"title":"Aggregation assisted synergism for the extraction of Am(III) by a polymer inclusion membrane containing mixed ligands: Extraction, spectroscopic and small-angle X-ray scattering study","authors":"Soumitra Panda , Bholanath Mahanty , Debasis Sen , Satish Mandal , Pramilla D. Sawant , Arunasis Bhattacharyya","doi":"10.1016/j.memsci.2026.125205","DOIUrl":"10.1016/j.memsci.2026.125205","url":null,"abstract":"<div><div>Generally, aggregation and synergism are common phenomenon in solvent extraction process when two amphiphilic extractants, one acidic and another neutral were employed for the metal ion extraction. Again, aggregation may drive the synergistic extraction of metal ions in a multi extractant system. However, to the best of our knowledge, the correlation between aggregation and synergism is unexplored in a more complex system like mixed extractant based polymeric plasticized membrane. Herein, we observed synergistic extraction of Am(III) from a dilute nitric acid solution (0.01–2 M) with a nitrophenyl octyl ether (NPOE) plasticized cellulose triacetate (CTA) based polymer inclusion membrane (PIM) containing an acidic extractant, di(2-ethylhexyl)phosphoric acid (D2EHPA) and a neutral extractant, <em>N,N,N′,N′</em>-tetraoctyldiglycolamide (TODGA). The Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), small angle X‐ray scattering (SAXS) and extraction studies indicate the involvement of both the ligand in the extraction of Eu(III) (considered as surrogate of Am(III)) and the evidence of aggregate formation in the structure of membrane. A possible mechanism was given to explain how aggregation synergistically assists in the extraction of metal ion based on the results from the SAXS studies. The self diffusion coefficients of Eu(III) was determined by non-stationary radiotracer diffusion method which nicely correlate with the size of the aggregate from SAXS studies of the membranes. The mixed membrane with a composition of D2EHPA and TODGA in the mole ratio of 2:1 follows the Langmuir isotherm model and pseudo second order kinetic model, both indicating a chemisorption process for the uptake of Eu(III) with a maximum uptake capacity of approximately 21 mg/g of PIM. The mixed membrane also employed for recovery of Am(III) from a filter paper waste sample which indicated ∼90 % recovery of the metal ion at 0.01 M HNO<sub>3</sub> indicating possible application of the developed synergistic PIM in the analysis of real samples.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"744 ","pages":"Article 125205"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075892","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 : 2026-04-01Epub Date: 2026-01-19DOI: 10.1016/j.memsci.2026.125180
Ahmed M.A. Abdelsamad , Ibrahim M.A. Elsherbiny , Mathias Kühnert , Marco Went , Anett Georgi , Stefan Panglisch , Agnes Schulze , Katrin Mackenzie
Per- and polyfluoroalkyl substances (PFAS) are a major threat to human health and the environment due to their persistence and harmfulness. One of the most efficient and sustainable approaches for their separation from water is membrane technology. In this study, polyelectrolyte multilayered (PEM) nanofiltration membranes were developed through layer-by-layer assembly of poly(diallyldimethylammonium chloride)/poly(styrenesulfonate) (PDADMAC/PSS) on polyethersulfone (PES) ultrafiltration supports to remove two representative PFAS, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA). The effects of bilayer number and electron beam (EB) surface modification of the PES support were systematically investigated. A membrane coated with two bilayers achieved a PFOA rejection of (90.0 ± 3.6)% with a pure water permeability of (19.6 ± 3.1) L m−2 h−1 bar−1 on unmodified PES, which improved to (94.5 ± 3.2)% and (25 ± 4) L m−2 h−1 bar−1 after EB modification. Increasing the coating to three bilayers further enhanced PFOA rejection to (99 ± 0.4)% with permeability of (16 ± 4.3) L m−2 h−1 bar−1, surpassing the commercial NF270 membrane with (94.6 ± 2.1)% and (15.7 ± 2.5) L m−2 h−1 bar−1). PFHxA rejection was slightly lower due to its smaller molecular size and lower hydrophobicity. The membranes maintained stable rejection across pH values, while salts, particularly MgSO4 with higher ionic strength, reduced rejection through charge screening and bilayer swelling, which also increased permeability. Overall, PEM membranes, especially those on EB-modified supports, provide a good balance between flux and selectivity and have great potential as scalable, energy-efficient methods of removing PFAS from water.
{"title":"Two-bilayer polyelectrolyte multilayered nanofiltration membranes for highly efficient removal of PFAS from water","authors":"Ahmed M.A. Abdelsamad , Ibrahim M.A. Elsherbiny , Mathias Kühnert , Marco Went , Anett Georgi , Stefan Panglisch , Agnes Schulze , Katrin Mackenzie","doi":"10.1016/j.memsci.2026.125180","DOIUrl":"10.1016/j.memsci.2026.125180","url":null,"abstract":"<div><div>Per- and polyfluoroalkyl substances (PFAS) are a major threat to human health and the environment due to their persistence and harmfulness. One of the most efficient and sustainable approaches for their separation from water is membrane technology. In this study, polyelectrolyte multilayered (PEM) nanofiltration membranes were developed through layer-by-layer assembly of poly(diallyldimethylammonium chloride)/poly(styrenesulfonate) (PDADMAC/PSS) on polyethersulfone (PES) ultrafiltration supports to remove two representative PFAS, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA). The effects of bilayer number and electron beam (EB) surface modification of the PES support were systematically investigated. A membrane coated with two bilayers achieved a PFOA rejection of (90.0 ± 3.6)% with a pure water permeability of (19.6 ± 3.1) L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> on unmodified PES, which improved to (94.5 ± 3.2)% and (25 ± 4) L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> after EB modification. Increasing the coating to three bilayers further enhanced PFOA rejection to (99 ± 0.4)% with permeability of (16 ± 4.3) L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>, surpassing the commercial NF270 membrane with (94.6 ± 2.1)% and (15.7 ± 2.5) L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>). PFHxA rejection was slightly lower due to its smaller molecular size and lower hydrophobicity. The membranes maintained stable rejection across pH values, while salts, particularly MgSO<sub>4</sub> with higher ionic strength, reduced rejection through charge screening and bilayer swelling, which also increased permeability. Overall, PEM membranes, especially those on EB-modified supports, provide a good balance between flux and selectivity and have great potential as scalable, energy-efficient methods of removing PFAS from water.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"744 ","pages":"Article 125180"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076323","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 : 2026-04-01Epub Date: 2026-02-04DOI: 10.1016/j.memsci.2026.125236
Morigen Zhao, Wen Liu, Jiashuo Fu, Wen Li, Sisi Cheng, Yunqi Li, Haining Wang, Shanfu Lu, Yan Xiang
Co-doping the proton exchange membrane with organophosphorus acid (OPA) and phosphoric acid (PA) as dual proton conductors can effectively enhance proton transport for high-temperature proton exchange membrane fuel cells (HT-PEMFCs). However, the influence of the OPA molecular structures on the proton transport remain unclear. Here we employ molecular dynamics simulations to investigate the effect of molecular steric effect on proton conduction behavior in polybenzimidazole-based membranes co-doped with OPA and PA as dual proton conductors. The interactions between these proton conductors and the polymer matrix are elucidated by investigating OPAs with varied carbon chains. The results reveal that longer carbon chains reduce electrostatic attraction and hydrogen bond binding energy, while decreasing total hydrogen bond density. This work provides atomistic-scale insights into the role of molecular steric effects on proton transport, offering guidance for designing advanced proton-conducting materials with balanced conductivity and stability.
{"title":"A molecular dynamics study on the steric effects of organophosphorus acid for proton exchange membranes","authors":"Morigen Zhao, Wen Liu, Jiashuo Fu, Wen Li, Sisi Cheng, Yunqi Li, Haining Wang, Shanfu Lu, Yan Xiang","doi":"10.1016/j.memsci.2026.125236","DOIUrl":"10.1016/j.memsci.2026.125236","url":null,"abstract":"<div><div>Co-doping the proton exchange membrane with organophosphorus acid (OPA) and phosphoric acid (PA) as dual proton conductors can effectively enhance proton transport for high-temperature proton exchange membrane fuel cells (HT-PEMFCs). However, the influence of the OPA molecular structures on the proton transport remain unclear. Here we employ molecular dynamics simulations to investigate the effect of molecular steric effect on proton conduction behavior in polybenzimidazole-based membranes co-doped with OPA and PA as dual proton conductors. The interactions between these proton conductors and the polymer matrix are elucidated by investigating OPAs with varied carbon chains. The results reveal that longer carbon chains reduce electrostatic attraction and hydrogen bond binding energy, while decreasing total hydrogen bond density. This work provides atomistic-scale insights into the role of molecular steric effects on proton transport, offering guidance for designing advanced proton-conducting materials with balanced conductivity and stability.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"745 ","pages":"Article 125236"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172331","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 : 2026-04-01Epub Date: 2026-02-03DOI: 10.1016/j.memsci.2026.125240
Wenbiao Ma , Jie Qiao , Qian Xu , Wei Shi , Peng Li , Xiao Du , Guoqing Guan , Xiaogang Hao
Inspired by the ship-locking transportation principle of the Panama Canal, this work developed a similar system based on an electrochemically switched ion permselective (SL-ESIP) separation device integrated with a free-standing electroactive membrane fabricated via a facile vacuum filtration method. This system mimics a multi-stage ion relay process by dynamically modulating liquid levels on both the feed and receiving sides, thereby effectively suppressing ion leakage and enabling efficient extraction, storage, and release of lithium ion (Li+). The designed carbon nanotubes/polyvinyl alcohol/Li1-xMn2O4 (CNTs/PVA/Li1-xMn2O4) composite membrane and device exhibited exhibited high compatibility within the SL-ESIP system when treating brines with extreme Mg/Li ratios up to ∼500. Notably, under optimized pulse conditions (30/60 min), the membrane achieved a high Li+/Mg2+ selectivity of 40.36 with a Li + flux of 0.055 mol m−2 h−1, outperforming the conventional electrochemically switched ion exchange (ESIX) process by 2.5-fold in flux while maintaining comparable selectivity. Moreover, by implementing a two-stage SL-ESIP operation, the overall Li+/Mg2+ separation performance of the system was further amplified to an apparent selectivity of 3353, demonstrating the feasibility and scalability of the SL-ESIP operation mode for subsequent lithium purification. Besides, molecular simulations reveal that Li1-xMn2O4 exhibits thermodynamically favored intercalation and kinetically accelerated diffusion for Li+, enabling high Li+ flux and exceptional Li+ selectivity over competing mono- and divalent ions in real Qarhan Salt Lake brines. This ship-locking transportation system-inspired electroactive membrane separation strategy offers a sustainable and efficient approach for the selective lithium extraction from high-salinity brines, and provides a versatile platform for the development of advanced ion-selective separation technologies.
{"title":"Panama Canal ship-locking transport system-inspired lithium ion recovery way based on an electrochemically switched free-standing membrane","authors":"Wenbiao Ma , Jie Qiao , Qian Xu , Wei Shi , Peng Li , Xiao Du , Guoqing Guan , Xiaogang Hao","doi":"10.1016/j.memsci.2026.125240","DOIUrl":"10.1016/j.memsci.2026.125240","url":null,"abstract":"<div><div>Inspired by the ship-locking transportation principle of the Panama Canal, this work developed a similar system based on an electrochemically switched ion permselective (SL-ESIP) separation device integrated with a free-standing electroactive membrane fabricated via a facile vacuum filtration method. This system mimics a multi-stage ion relay process by dynamically modulating liquid levels on both the feed and receiving sides, thereby effectively suppressing ion leakage and enabling efficient extraction, storage, and release of lithium ion (Li<sup>+</sup>). The designed carbon nanotubes/polyvinyl alcohol/Li<sub>1-x</sub>Mn<sub>2</sub>O<sub>4</sub> (CNTs/PVA/Li<sub>1-x</sub>Mn<sub>2</sub>O<sub>4</sub>) composite membrane and device exhibited exhibited high compatibility within the SL-ESIP system when treating brines with extreme Mg/Li ratios up to ∼500. Notably, under optimized pulse conditions (30/60 min), the membrane achieved a high Li<sup>+</sup>/Mg<sup>2+</sup> selectivity of 40.36 with a Li <sup>+</sup> flux of 0.055 mol m<sup>−2</sup> h<sup>−1</sup>, outperforming the conventional electrochemically switched ion exchange (ESIX) process by 2.5-fold in flux while maintaining comparable selectivity. Moreover, by implementing a two-stage SL-ESIP operation, the overall Li<sup>+</sup>/Mg<sup>2+</sup> separation performance of the system was further amplified to an apparent selectivity of 3353, demonstrating the feasibility and scalability of the SL-ESIP operation mode for subsequent lithium purification. Besides, molecular simulations reveal that Li<sub>1-x</sub>Mn<sub>2</sub>O<sub>4</sub> exhibits thermodynamically favored intercalation and kinetically accelerated diffusion for Li<sup>+</sup>, enabling high Li<sup>+</sup> flux and exceptional Li<sup>+</sup> selectivity over competing mono- and divalent ions in real Qarhan Salt Lake brines. This ship-locking transportation system-inspired electroactive membrane separation strategy offers a sustainable and efficient approach for the selective lithium extraction from high-salinity brines, and provides a versatile platform for the development of advanced ion-selective separation technologies.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"745 ","pages":"Article 125240"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172339","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 : 2026-04-01Epub Date: 2026-02-07DOI: 10.1016/j.memsci.2026.125257
Xiaohu Zhai , Xianfeng Li , Xuesong Li, Zhiwei Wang
Precisely regulating the aqueous-phase diffusion and interfacial mass transfer processes of the amine monomers remains a key strategy for fabricating high-performance nanofiltration (NF) membranes. However, current approaches to interfacial polymerization still face significant challenges such as the single function of regulators, complex regulation systems, and high costs. Herein, we propose a novel approach for regulating interfacial polymerization processes with the use of dual-functional regulators. Specifically, tetraethylammonium chloride (TEACl) is employed as a dual-functional regulator, which significantly reduces the polyamide layer thickness while enhancing its cross-linking degree and uniformity. This is achieved through the synergistic regulation of the diffusion and trans-interface processes of amine monomers. Compared to the control membrane, NF membranes prepared with the TEACl-assisted interfacial polymerization process exhibit a more than 500% increase in permeability (from 5.6 L m-2h-1bar-1 to 33.5 L m-2h-1bar-1), while retaining comparable Na2SO4 rejection performance (>98%) and demonstrating excellent anti-scaling properties. Notably, the membranes fabricated using this innovative strategy also show high retention of emerging contaminants (ECs) and low retention of divalent cations, facilitating the selective removal of harmful substances from water while preserving essential minerals. The TEACl-regulated membrane also demonstrates excellent long-term operational stability. This novel interfacial polymerization regulation strategy provides a new paradigm for the fabrication of high-performance NF membranes.
精确调控胺类单体的水相扩散和界面传质过程是制备高性能纳滤膜的关键策略。然而，目前的界面聚合方法仍然面临着监管机构功能单一、监管系统复杂和成本高等重大挑战。在此，我们提出了一种使用双功能调节剂调节界面聚合过程的新方法。其中，四乙基氯化铵（TEACl）作为双功能调节剂，可显著降低聚酰胺层厚度，同时提高交联度和均匀性。这是通过胺单体的扩散和跨界面过程的协同调节来实现的。与对照膜相比，用teacl辅助界面聚合工艺制备的NF膜的渗透率增加了500%以上（从5.6 L m-2h-1bar-1增加到33.5 L m-2h-1bar-1），同时保持了相当的Na2SO4截留性能（>98%），并表现出优异的抗结垢性能。值得注意的是，使用这种创新策略制备的膜还显示出对新出现的污染物（ECs）的高截留率和对二价阳离子的低截留率，促进了水中有害物质的选择性去除，同时保留了必需矿物质。teacl调控膜也表现出良好的长期操作稳定性。这种新型的界面聚合调控策略为高性能纳滤膜的制备提供了新的范例。
{"title":"Enhancing water purification and anti-scaling performance of nanofiltration membranes: A novel interfacial polymerization regulation strategy based on dual-functional regulators","authors":"Xiaohu Zhai , Xianfeng Li , Xuesong Li, Zhiwei Wang","doi":"10.1016/j.memsci.2026.125257","DOIUrl":"10.1016/j.memsci.2026.125257","url":null,"abstract":"<div><div>Precisely regulating the aqueous-phase diffusion and interfacial mass transfer processes of the amine monomers remains a key strategy for fabricating high-performance nanofiltration (NF) membranes. However, current approaches to interfacial polymerization still face significant challenges such as the single function of regulators, complex regulation systems, and high costs. Herein, we propose a novel approach for regulating interfacial polymerization processes with the use of dual-functional regulators. Specifically, tetraethylammonium chloride (TEACl) is employed as a dual-functional regulator, which significantly reduces the polyamide layer thickness while enhancing its cross-linking degree and uniformity. This is achieved through the synergistic regulation of the diffusion and <em>trans</em>-interface processes of amine monomers. Compared to the control membrane, NF membranes prepared with the TEACl-assisted interfacial polymerization process exhibit a more than 500% increase in permeability (from 5.6 L m<sup>-2</sup>h<sup>-1</sup>bar<sup>-1</sup> to 33.5 L m<sup>-2</sup>h<sup>-1</sup>bar<sup>-1</sup>), while retaining comparable Na<sub>2</sub>SO<sub>4</sub> rejection performance (>98%) and demonstrating excellent anti-scaling properties. Notably, the membranes fabricated using this innovative strategy also show high retention of emerging contaminants (ECs) and low retention of divalent cations, facilitating the selective removal of harmful substances from water while preserving essential minerals. The TEACl-regulated membrane also demonstrates excellent long-term operational stability. This novel interfacial polymerization regulation strategy provides a new paradigm for the fabrication of high-performance NF membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"745 ","pages":"Article 125257"},"PeriodicalIF":9.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172379","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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