Journal of Membrane Science最新文献

Highly selective separation of yttrium from heavy rare earth elements by hollow fiber renewal liquid membrane 中空纤维再生液膜对钇和重稀土元素的高选择性分离

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-11 DOI: 10.1016/j.memsci.2025.125054

Tingting Tang , Wenyi Zhang , Yucheng Liu , Xuewei Li , Kaibo Hu , Yinhua Wan , Jiuyang Lin

Yttrium (Y), the most abundant heavy rare earth element (HREE) in ion-adsorption type rare earth ores (IATREO), is essential for various innovative functional materials. This study employed hollow fiber renewal liquid membrane (HFRLM) technology combined with a novel phosphorus-containing extractant Cextrant322 (C322) to establish a C322-HFRLM system for the selective separation of Y³⁺ from Y-rich HREEs solution of IATREO. Under the optimized conditions of 0.5 mol L⁻¹ C322, feed phase pH of 3, flow rate of 550 mL min⁻¹, and stripping-to-feed volume ratio (V_S/V_F) of 1.6, the results demonstrated that the purity of Y³⁺ in the feed phase increased from 61.90 % to 97.69 % after a single-step simultaneous extraction-stripping process. The maximum separation factor (SF) values between Ho³⁺-Lu³⁺ and Y³⁺ (i.e., SF_Ho/Y, SF_Er/Y, SF_Tm/Y, SF_Yb/Y, and SF_Lu/Y) were 1.32, 2.41, 5.71, 8.60, and 9.80 at 0.25-h operation, respectively. Compared with the traditional hollow fiber supported liquid membrane (HFSLM) system, the C322-HFRLM system achieved 1.29 times increase in Y³⁺ purity, demonstrating significantly enhanced separation efficiency and stability. Therefore, HFRLM presents substantial potential as an advanced membrane separation technology for the efficient industrial-scale separation and enrichment of Y³⁺.

钇(Y)是离子吸附型稀土矿（IATREO）中含量最多的重稀土元素（HREE），是各种创新功能材料必不可少的元素。本研究采用中空纤维更新液膜（HFRLM）技术结合新型含磷萃取剂Cextrant322 (C322)，建立C322-HFRLM体系，用于从IATREO富y HREEs溶液中选择性分离Y3+。结果表明，在0.5 mol L−1 C322、进料相pH = 3、流量为550 mL min−1、提料体积比（VS/VF）为1.6的优化条件下，经单步同步提提，进料相中Y3+的纯度由61.90%提高到97.69%。在0.25 h时，Ho3+-Lu3+与Y3+的最大分离因子（SF）值（SFHo/Y、SFEr/Y、SFTm/Y、SFYb/Y和SFLu/Y）分别为1.32、2.41、5.71、8.60和9.80。与传统的中空纤维支撑液膜（HFSLM）体系相比，C322-HFRLM体系的Y3+纯度提高了1.29倍，分离效率和稳定性显著提高。因此，HFRLM作为一种先进的膜分离技术具有很大的潜力，可以用于工业规模的高效分离和富集Y3+。

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引用次数: 0

3D polyphenol-intercalated covalent organic framework membranes: Toward interlayer manipulation for high-permeability nanofiltration 三维多酚嵌层共价有机框架膜：用于高渗透纳滤的层间操作

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-10 DOI: 10.1016/j.memsci.2025.125050

Lei Huang , Xueting Zhao , Jinmao Lv , Xinliang Zhang , Zhihong Dong , Anqi Liu , Jiefeng Pan , Xiaocheng Lin

Controllable assembly of covalent organic framework (COF) nanosheets into two-dimensional (2D) layered membranes is crucial to prepare advanced membranes. However, the prevalence of disordered stacking of COF nanosheets often leads to tortuous or overlapped pores and sacrifices membrane permeability. Further, membrane stability is often questioned due to weak interlayer interactions. Herein, a three-dimensional (3D) polyphenol-mediated interlayer engineering strategy was proposed for manipulating the interlayer channels and interactions of COF membranes for simultaneous enhancement of membrane permeability and stability. The COF membranes (TTSBI/TFTA-TG_(Cl)) were prepared via vacuum-assisted self-assembly method with TFTA-TG_(Cl) COF nanosheets as the building host and 3D polyphenols 5,5′,6,6′-Tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane (TTSBI) as intercalating guests. The stereoscopic spirocyclic architecture of TTSBI provides rigid interlayer support to expand the 2D nanochannels within the COF membranes, which optimizes the water molecule transport pathway to enhance water permeance. The multiple interactions (e.g., electrostatic and cation-π interactions) between TTSBI and COF nanosheets strengthen the interlayer combination, thereby enhancing the structural stability of the COF membrane. The as-prepared TTSBI/TFTA-TG_(Cl) membrane exhibited water permeance of 77.3 L m⁻² h⁻¹·bar⁻¹ (approximately 2.5 times that of the pristine TFTA-TG_(Cl) membrane) with methylene blue rejection above 91 %. Furthermore, the TTSBI/TFTA-TG_(Cl) membrane can effectively reject dye molecules with molecular weight of ≥800 Da, and simultaneously demonstrate superior stability. This polyphenol-mediated interlayer engineering strategy may provide new insights into the construction and manipulation of the channels in COF membranes for high-permeability separation application.

将共价有机骨架（COF）纳米片可控组装成二维（2D）层状膜是制备先进膜的关键。然而，COF纳米片无序堆积的普遍存在往往导致扭曲或重叠的孔隙和牺牲膜的通透性。此外，由于层间相互作用弱，膜的稳定性经常受到质疑。本文提出了一种三维（3D）多酚介导的层间工程策略，用于操纵COF膜的层间通道和相互作用，同时增强膜的通透性和稳定性。采用真空辅助自组装法，以tft - tg (Cl) COF纳米片为构建主体，以三维多酚5,5 ',6,6 ' -四羟基-3,3,3 ',3 ' -四甲基-1,1 ' -螺比茚（TTSBI）为插入物，制备了COF膜（TTSBI/ tft - tg (Cl)）。TTSBI的立体螺旋环结构为扩展COF膜内的二维纳米通道提供了刚性层间支撑，从而优化了水分子的运输途径，增强了水渗透能力。TTSBI与COF纳米片之间的多重相互作用（如静电和阳离子-π相互作用）加强了层间结合，从而提高了COF膜的结构稳定性。制备的TTSBI/ ttfta - tg （Cl）膜的透水性为77.3 L m−2 h−1·bar−1（约为原始ttfta - tg （Cl）膜的2.5倍），亚甲蓝截留率达91%以上。此外，TTSBI/ ttfta - tg （Cl）膜可以有效地排斥分子量≥800 Da的染料分子，同时表现出优异的稳定性。这种多酚介导的层间工程策略可能为COF膜中通道的构建和操作提供新的见解，用于高渗透分离应用。

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引用次数: 0

Preparation of polysulfone-based imidazole-functionalized self-crosslinked anion exchange membranes for electrodialysis 电渗析用聚砜基咪唑功能化自交联阴离子交换膜的制备

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-09 DOI: 10.1016/j.memsci.2025.125019

Jinmao Lv , Xueting Zhao , Lei Huang , Xuexi Zhang , Yu Sun , Jiefeng Pan , Xiaocheng Lin

Electrodialysis technology, an energy-efficient membrane separation technique, relies on the performance of its core component—ion exchange membranes (IEMs). However, anion exchange membranes (AEMs) still lag behind cation exchange membranes (CEMs, e.g., Nafion), primarily due to the trade-off between minimizing area resistance and maintaining dimensional stability. To tackle this issue, we leveraged 1-vinylimidazole (1-VIm) as a dual-functional agent by grafting it onto chloromethylated polysulfone (CMPSF) via N-alkylation and subsequently employing its vinyl group for in-situ self-polymerization to form the crosslinked structure. Results demonstrate that the 1-VIm self-crosslinked structure enables the coexistence of a high ion exchange capacity (IEC) for low area resistance and outstanding dimensional stability (suppressed swelling). The optimal VIPSF-3 membrane exhibits a swelling ratio of only 8.0 ± 0.5 % at 60 °C, while significantly enhancing membrane selectivity with an ion transport number (

t_{i}

) as high as 0.990 ± 0.002. During a 140-min electrodialysis desalination test, the optimized VIPSF-3 membrane outperformed the commercial AMV AEM by achieving a salt removal rate (

R_{s a l t}

) of 90.5 ± 0.8 %, a current efficiency (η) of 98.3 ± 0.8 %, and an energy consumption (EC) of 4.04 ± 0.13 kWh·kg⁻¹. These values surpass those of AMV (

R_{s a l t}

= 82.4 ± 1.0 %, η = 88.3 ± 1.1 %, EC = 5.20 ± 0.17 kWh·kg⁻¹). This study provides a novel strategy for preparing high-performance AEMs for electrodialysis applications.

电渗析技术是一种高效节能的膜分离技术，其核心部件离子交换膜（IEMs）的性能是电渗析技术的关键。然而，阴离子交换膜（AEMs）仍然落后于阳离子交换膜（CEMs，如Nafion），主要是因为要在最小化面积电阻和保持尺寸稳定性之间进行权衡。为了解决这一问题，我们利用1-乙烯基咪唑（1-VIm）作为双功能剂，通过n-烷基化将其接枝到氯甲基化聚砜（CMPSF）上，随后利用其乙烯基进行原位自聚合形成交联结构。结果表明，1-VIm自交联结构使高离子交换容量（IEC）的共存具有低面积电阻和突出的尺寸稳定性（抑制膨胀）。优化后的VIPSF-3膜在60℃下的溶胀率仅为8.0±0.5%，同时膜的选择性显著提高，离子传递数（ti）高达0.990±0.002。在140 min的电渗析脱盐试验中，优化后的VIPSF-3膜的脱盐率（Rsalt）为90.5±0.8%，电流效率（η）为98.3±0.8%，能耗（EC）为4.04±0.13 kWh·kg−1，优于商用AMV AEM。这些值超过lamv (Rsalt = 82.4±1.0%,η= 88.3±1.1%,EC = 5.20±0.17千瓦时·公斤−1)。本研究为制备用于电渗析的高性能AEMs提供了一种新的策略。

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引用次数: 0

Advancing gas separation performance: Plasma-treated polymer from 5-ethylidene-2-norbornene beyond the Robeson upper bound 推进气体分离性能：等离子体处理的5-乙基-2-降冰片烯聚合物，超过罗布森上限

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-09 DOI: 10.1016/j.memsci.2025.125039

Daria Syrtsova , Alexandr Zinoviev , Alyona Wozniak , Maxim Bermeshev , Elena Skryleva , Roman Nikiforov , Mikhail Piskarev , Alexander Кuznetsov , Alexandr Alentiev , Alla Gilman , Victoria Ryzhikh

Low-temperature plasma treatment is demonstrated as an effective strategy to enhance the gas separation performance of a vinyl-addition polymer synthesized from the industrially available monomer 5-ethylidene-2-norbornene (APENB). The plasma modification introduces controlled surface and near-surface functionalities without compromising the bulk integrity of the polymer matrix. Structural and physicochemical analyses (XPS, FTIR, AFM) confirmed the incorporation of polar functional groups into the surface layer, resulting in a significantly improved permeability–selectivity balance. A systematic investigation of air plasma treatment conditions revealed the optimal parameters for enhancing gas transport performance. A 30-s plasma exposure was found to be optimal, yielding a more than twofold increase in O₂/N₂ selectivity and over a 20-fold enhancement in He/CH₄ and H₂/CH₄ selectivity. Aging studies over a one-month period showed that the improved transport properties remained stable, with the H₂/CH₄ performance of treated polymer exceeding the 2015 Robeson upper bound. This work highlights the potential of plasma-based surface engineering to unlock advanced transport properties in commercially viable membrane materials for industrial gas separation.

低温等离子体处理是提高乙烯基加成聚合物气体分离性能的有效策略，该聚合物是由工业上可用的单体5-乙基-2-降冰片烯（APENB）合成的。等离子体修饰引入了受控的表面和近表面功能，而不影响聚合物基体的整体完整性。结构和物理化学分析（XPS， FTIR， AFM）证实了极性官能团在表层的掺入，从而显著改善了渗透-选择性平衡。对空气等离子体处理条件的系统研究揭示了提高气体传输性能的最佳参数。30s的血浆暴露是最佳的，O2/N2选择性提高了两倍以上，He/CH4和H2/CH4选择性提高了20倍以上。经过一个月的老化研究表明，改善后的聚合物输运性能保持稳定，处理后的聚合物的H2/CH4性能超过了2015年Robeson上限。这项工作强调了基于等离子体的表面工程的潜力，以解锁商业上可行的用于工业气体分离的膜材料的先进传输特性。

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引用次数: 0

Ultra-microporosity enabled by the branched polybenzimidazole ion-solvating membranes for high performance alkaline water electrolysis 支化聚苯并咪唑离子溶剂化膜实现了高性能碱性电解的超微孔隙

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-09 DOI: 10.1016/j.memsci.2025.125045

Zitong Huang , Kai wang , Ruofei Gao , Yi Cheng , Xinxin Li , Jinhua Ji , Xiaomeng Chu , Shaojie Liu , Nanwen Li

Ion-solvating membranes (ISMs) with high ionic conductivity and robust chemical stability are essential for high-performance alkaline water electrolysis (AWE). While naphthalene-based polybenzimidazoles (NPBI) demonstrate promising stability, their OH⁻ conductivity remains limited due to insufficient electrolyte uptake and poorly organized ion transport pathways. To address this limitation, we developed a series of branched NPBI copolymers (NPBI-BM-x) through strategic incorporation of rigid tricarboxylic acid comonomers. This molecular design introduces rigid or articulated branching centers that disrupt chain packing and generate uniformly and continuously distributed ultra-micropores (0.54–0.58 nm), as confirmed by CO₂ adsorption, XRD, and simulation. The tailored ultra-microporosity provide large free volume within the membrane, which significantly enhancing KOH absorption and facilitating rapid hydroxide transport. The optimized membrane NPBI-BM₂-6 achieves a KOH uptake of 99.8 wt% and an OH⁻ conductivity of 225 mS/cm at 80 °C in 6 M KOH which is 1.9 times higher than that of the linear NPBI. When integrated into an AWE cell with non-noble catalysts, the membrane enables a current density of 2.5 A/cm² at 2.0 V and 80 °C (even achieved 3.58 A/cm² 90 °C) and voltage remained stable in a 685 h test. This branched ultra-microporous molecularly engineered architecture unlocks durable, high-performance alkaline water electrolysis.

离子溶剂化膜（ISMs）具有高离子电导率和强大的化学稳定性，是高性能碱性电解（AWE）的必要条件。虽然萘基多苯并咪唑（NPBI）表现出良好的稳定性，但由于电解质摄取不足和离子运输途径组织不良，它们的OH -电导率仍然有限。为了解决这一限制，我们通过战略性地加入刚性三羧酸共聚物，开发了一系列支链NPBI共聚物（NPBI- bm -x）。这种分子设计引入了刚性或铰接的分支中心，破坏了链式包装，产生了均匀连续分布的超微孔（0.54-0.58 nm），这一点得到了CO2吸附、XRD和模拟的证实。定制的超微孔提供了大的膜内自由体积，显著增强了KOH的吸收，促进了氢氧化物的快速运输。优化后的NPBI- bm2 -6膜的KOH吸收率为99.8 wt%，在80°C、6 M KOH条件下的OH -电导率为225 mS/cm，是线性NPBI膜的1.9倍。当与非贵金属催化剂集成到AWE电池中时，该膜在2.0 V和80°C时的电流密度为2.5 a /cm2(90°C时甚至达到3.58 a /cm2)，并且在685小时的测试中电压保持稳定。这种分支的超微孔分子工程结构开启了持久、高性能的碱性电解。

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引用次数: 0

Bimetallic engineering in Ag/Zn-ZIF-8/Pebax mixed matrix membranes for enhanced CO2 separation 双金属工程在Ag/Zn-ZIF-8/Pebax混合基质膜中的应用

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-08 DOI: 10.1016/j.memsci.2025.125046

Qian-Qian Li, Yang Li, Heng Mao, Yan-Mei Zhang, Qiu-Ying Zhang, Xin-Ru Chen, Zi-Cong Shan, Xian-Zhe Zhou, Li-Hao Xu, Zhi-Ping Zhao

Mixed matrix membranes (MMMs) have emerged as a critical platform for molecular separation, especially carbon capture from point-emission sources. In this study, a series of novel MMMs were fabricated by incorporating the bimetallic Ag/Zn-ZIF-8 nanoparticles into the poly (ether-block-amide) (Pebax) matrix for efficient CO₂/N₂ separation. The SEM, EDS, XRD, FTIR, XPS, TGA, N₂ adsorption-desorption measurements were employed to elucidate the microstructures and physicochemical properties of the resultant nanoparticles and membranes. The bimetallic coordination-induced optimization modulated the inherent structure of ZIF-8 framework and enhanced CO₂ affinity, thereby forming the CO₂-selective transport channels over N₂. The incorporation of Ag ⁺ promoted the uniform dispersion of Ag/Zn-ZIF-8 nanoparticles in Pebax matrix, indicating the excellent polymer-filler interfacial compatibility. Impressively, the resulting membrane achieved the superior separation performance with a CO₂ permeability of 359 Barrer and a CO₂/N₂ selectivity of 53, which were 2.5 and 1.4 times higher than that of the pristine Pebax membrane. Besides, the introduction of Ag/Zn-ZIF-8 nanoparticles enhanced the thermal and mechanical stability of the membrane, ensuring the potential for long-term operation. These findings herein advance the rational design and preparation of high-performance MMMs for sustainable carbon capture.

混合基质膜（MMMs）已成为分子分离的重要平台，特别是从点发射源捕获碳。在本研究中，通过将双金属Ag/Zn-ZIF-8纳米颗粒掺入聚醚-嵌段酰胺（Pebax）基质中，制备了一系列新型的MMMs，用于高效的CO2/N2分离。采用SEM、EDS、XRD、FTIR、XPS、TGA、N2吸附-脱附等测试手段对纳米颗粒和膜的微观结构和理化性质进行了表征。双金属配位诱导的优化调节了ZIF-8骨架的固有结构，增强了其对CO2的亲和力，从而形成了N2上的CO2选择性转运通道。Ag +的掺入促进了Ag/Zn-ZIF-8纳米颗粒在Pebax基体中的均匀分散，表明其具有良好的聚合物-填料界面相容性。令人印象深刻的是，该膜具有优异的分离性能，其CO2渗透率为359 Barrer， CO2/N2选择性为53，分别是原始Pebax膜的2.5和1.4倍。此外，Ag/Zn-ZIF-8纳米颗粒的引入增强了膜的热稳定性和机械稳定性，确保了膜的长期运行潜力。这些发现为可持续碳捕获的高性能MMMs的合理设计和制备提供了依据。

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引用次数: 0

Integrating protein into covalent organic framework nanochannel membranes for highly enantioselective transport 将蛋白质整合到共价有机框架纳米通道膜中进行高对映选择性运输

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-08 DOI: 10.1016/j.memsci.2025.125044

Lei Yang , Yuning Feng , Yue Sun

The construction of highly efficient and selective solid-state nanochannels for chiral separation remains a formidable challenge. In this study, we developed a hybrid membrane by incorporating myoglobin (Mb) into the nanochannels of covalent organic frameworks (COFs) through in situ growth and subsequent biofunctionalization. The resulting Mb-COF composite membrane exhibited well-ordered nanochannels with exceptional chiral recognition capability. It achieved outstanding enantioselectivity (ee = 96.4 %) and high permeation flux (367 μmol m⁻² h⁻¹) toward S-ibuprofen (S-PRF), significantly surpassing the performance of unmodified COF membrane. The membrane also demonstrated remarkable stability and reproducibility under operational conditions. Furthermore, we provide mechanistic insights into the chiral transport process, highlighting the role of protein-substrate interactions within the confined nanochannels. This work not only offers a novel strategy for designing high-performance chiral separation membranes but also advances our understanding of enantioselective transport mechanisms in biomimetic environments. The Mb-COF platform holds great promise for applications in chiral drug purification and analytical chemistry.

构建高效、选择性的固体纳米通道用于手性分离仍然是一个艰巨的挑战。在这项研究中，我们通过原位生长和随后的生物功能化，将肌红蛋白（Mb）结合到共价有机框架（COFs）的纳米通道中，开发了一种杂交膜。得到的Mb-COF复合膜具有有序的纳米通道和优异的手性识别能力。对s -布洛芬（S-PRF）具有良好的对映选择性（ee = 96.4%）和较高的渗透通量（367 μmol m−2 h−1），明显优于未改性的COF膜。该膜在操作条件下也表现出良好的稳定性和重复性。此外，我们提供了手性运输过程的机制见解，强调了蛋白质-底物相互作用在受限纳米通道中的作用。这项工作不仅为设计高性能手性分离膜提供了一种新的策略，而且还促进了我们对仿生环境中对映选择性转运机制的理解。Mb-COF平台在手性药物纯化和分析化学方面具有很大的应用前景。

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引用次数: 0

New approach to 3D-print methacrylic acid/polyethylene glycol diacrylate-based membranes based on polymerization induced phase separation 基于聚合诱导相分离的3d打印甲基丙烯酸/聚乙二醇双丙烯酸酯基膜的新方法

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-08 DOI: 10.1016/j.memsci.2025.125047

Haleh Nourizadeh Kazerouni, Gabriel Toshiaki Tayama, Julie Fréchette, Younès Messaddeq

We present a novel freeform fabrication strategy for polymer membranes via 3D printing, in which porosity is generated through a polymerization-induced phase separation mechanism. The approach employs a vat-photopolymerization compatible formulation to produce a macroporous network with coexisting mesoporosity. Hydrophilic flat-sheet membranes (400 μm thick) were fabricated and subjected to post-treatments involving CO₂ supercritical drying and solvent exchange. The resulting membranes exhibited permeance of up to 36 and 29 LMH.bar⁻¹, respectively, under a transmembrane pressure of 2 bar. An in-depth evaluation was conducted on membranes produced from photocurable formulations containing methacrylic acid (MA, 30 vol%) and polyethylene glycol diacrylate (PEGDA, 20 vol%), with varying ratios of 1-butanol and 2-phenoxyethanol as porogens. SEM analysis revealed a porous morphology throughout the membrane cross-section. The top-performing sample exhibited the highest specific surface area of 12.8 m²/g and the smallest mean pore diameters of 45 nm and 42 nm, as determined by adsorption branches of Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) analyses, respectively. Pore size distribution was compared with liquid-liquid displacement method, which revealed mean pore size of 8.8 nm, with a small quantity of pores of approximately 121 nm, which were in better agreement with pure water flux values. The influence of post-polymerization porogen removal methods—solvent exchange and supercritical drying—was also assessed. Post-treated membranes demonstrated lower compaction factors and more stable flux over time and under increasing pressure. This technique offers a promising route for the customized design of membrane geometries and architectures tailored to specific separation challenges. We further demonstrate such concept by printing textured membranes with wavy and rugged surface profiles.

我们提出了一种新的自由曲面聚合物膜的3D打印制造策略，其中孔隙是通过聚合诱导的相分离机制产生的。该方法采用了一种与光聚合相容的配方，以产生具有共存介孔的大孔网络。制备了400 μm厚的亲水性平板膜，并进行了CO2超临界干燥和溶剂交换后处理。所得膜的通透率高达36和29 LMH。在2bar的跨膜压力下，分别为Bar−1。对含有甲基丙烯酸（MA, 30 vol%）和聚乙二醇二丙烯酸酯（PEGDA, 20 vol%）、不同比例的1-丁醇和2-苯氧乙醇作为多孔剂的光固化配方制备的膜进行了深入评估。扫描电镜分析显示，多孔形态贯穿整个膜的横截面。通过吸附分支brunauer - emmet - teller （BET）和Barrett-Joyner-Halenda （BJH）分析，表现最佳的样品具有最高的12.8 m2/g比表面积和最小的平均孔径，分别为45 nm和42 nm。与液-液置换法进行孔径分布比较，平均孔径为8.8 nm，少量孔径约为121 nm，与纯水通量值吻合较好。评价了溶剂交换法和超临界干燥法对聚合后气孔去除效果的影响。经过处理的膜表现出较低的压实系数和更稳定的通量随着时间的推移和压力的增加。这项技术为定制膜的几何形状和结构提供了一条有前途的途径，以适应特定的分离挑战。我们通过打印具有波浪形和崎岖表面轮廓的纹理膜进一步证明了这一概念。

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引用次数: 0

Dopamine-bridged CuS–ZnIn2S4/PAN nanofibrous membrane for purification of viscous emulsified oil pollutants with integrated oil resistance, photocatalytic self-cleaning, and photothermal conversion 多巴胺桥接cu - znin2s4 /PAN纳米纤维膜净化粘性乳化油污染物，集耐油、光催化自清洁和光热转化于一体

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-08 DOI: 10.1016/j.memsci.2025.125030

Jie Liu , Yingqing Zhan , Xinyue Duan , Jing Yang , Yuxing Han , Yajie Lei , Sihan Li , Hongyi Zhang

The polymeric membrane encounters huge challenge in dealing with high-viscosity oil pollutants and complicated membrane fouling issues. Herein, the multi-functional polymeric composite membrane (ZCP) is fabricated via anchoring bio-adhesive dopamine bridged gear-like CuS–ZnIn₂S₄ heterostructure onto PAN nanofiber support, which hits three birds with one stone. Firstly, the unique three-dimensional gear-like structure confers the ultra-low oil adhesion and high permeability to membrane by constructing underwater superoleophobicity (UWCA: up to 157.1° ± 1.6°) and providing efficient mass transfer channels, as confirmed by Molecular dynamics simulation and Hermia equation-fitted blocking models. The ZCP membrane demonstrates superior separation flux (3921.44 ± 196.1 L m⁻² h⁻¹) and separation efficiency (up to 99.53 %) for diverse oil-in-water emulsions. Besides, the ZCP membrane shows remarkable durability in harsh conditions and cyclic separation stability. Secondly, dopamine bridged CuS–ZnIn₂S₄ heterostructure mitigates charge recombination, strengthens electron transfer, and extends light absorption, which results in favorable photocatalytic self-cleaning via peroxymonosulfate (PMS) activation. Under simulated sunlight and low PMS input, the ZCP membrane exhibits high-efficiency catalytic degradation of organic pollutants within 60 min (97.9 % tetracycline and 100 % dye degradation rates) and effective self-cleaning for membrane regeneration (98.51 ± 2.4 % flux recovery rate). Moreover, the band structure, charge transfer, and mechanism of photocatalytic PMS activation are elucidated. Thirdly, owing to the photothermal conversion function of CuS–ZnIn₂S₄ heterostructure, the membrane surface temperature reaches 61.7 °C within 15 s, thus efficiently reducing oil viscosity and achieving 102.04 % enhancement in permeation flux during the simulated O/W separation application. This work opens a new avenue for treatment of complex emulsified oily wastewater and membrane fouling control.

聚合物膜在处理高粘度油类污染物和复杂的膜污染问题方面面临着巨大的挑战。本研究通过在PAN纳米纤维载体上锚定生物胶多巴胺桥接齿轮状cu - znin2s4异质结构，制备了多功能聚合物复合膜（ZCP），实现了一举三得的效果。首先，独特的三维齿轮状结构通过构建水下超疏油性（UWCA：高达157.1°±1.6°）和提供高效的传质通道，为膜提供了超低的油粘附性和高渗透性，分子动力学模拟和Hermia方程拟合阻塞模型证实了这一点。ZCP膜对多种水包油乳剂具有较好的分离通量（3921.44±196.1 L m−2 h−1）和分离效率（高达99.53%）。ZCP膜具有良好的耐久性能和循环分离稳定性。其次，多巴胺桥接的cu - znin2s4异质结构减轻了电荷重组，加强了电子转移，扩大了光吸收，从而通过过氧单硫酸盐（PMS）活化产生了良好的光催化自清洁。在模拟阳光和低PMS输入条件下，ZCP膜在60 min内对有机污染物具有高效的催化降解（四环素降解率97.9%，染料降解率100%）和有效的自清洁再生膜（通量回收率98.51±2.4%）。此外，还研究了光催化PMS活化的能带结构、电荷转移和机理。第三，由于cu - znin2s4异质结构的光热转换功能，膜表面温度在15 s内达到61.7℃，从而有效降低了油的粘度，在模拟油水分离应用过程中，渗透通量提高了102.04%。本研究为复杂乳化含油废水的处理和膜污染控制开辟了新的途径。

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引用次数: 0

In-situ construction of ZIF-embedded hydrogel electro-driven membranes for lithium selectivity 原位构建zif包埋水凝胶电驱动锂选择性膜

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-12-08 DOI: 10.1016/j.memsci.2025.125043

Yangbo Qiu , Yidong Gao , Jingxiang Rockson Liu , Yuantian Cai , Ying Mei , Lei Xia , How Yong Ng , Yan Zhao , Bart Van der Bruggen , Chuyang Tang

Electro-driven membranes with monovalent ion selectivity represent a promising technology for sustainable lithium (Li) recovery from spent lithium-ion battery (LIB) leachate. However, existing membranes suffer from limited Li⁺ selectivity and low ion permeation rates. In this study, a zeolitic imidazolate framework (ZIF)-embedded hydrogel electro-driven membrane was developed for selective Li⁺ extraction via electrodialysis (ED). A poly(dimethyl diallyl ammonium chloride) (PDDA) network-threaded ZIF (QZIF) layer was in-situ constructed within the hydrogel matrix of Kevlar aramid nanofibers (KANFs), forming a stable composite layer on a sulfonated polysulfone (SPSF) substrate. Benefiting from the synergistic effects of size sieving and electrostatic repulsion, the resulting QZIF@KANF#SPSF membrane exhibited rapid Li⁺ transport while effectively rejecting larger divalent ions (Ni²⁺, Co²⁺, and Mn²⁺). During ED at 5 mA cm⁻², the QZIF@KANF#SPSF membrane achieved a Li⁺ permeation rate of 0.45 mol m⁻² h⁻¹ in a 25 mM Li⁺, Ni²⁺, Co²⁺, and Mn²⁺ mixed solution, with high permselectivities of 13.8, 12.2, and 10.5 for Li⁺/Ni²⁺, Li⁺/Co²⁺, and Li⁺/Mn²⁺, respectively. This strategy of embedding charged ZIFs within a hydrogel matrix provides a robust and scalable pathway for enhancing Li⁺ selectivity and transport efficiency in advanced separation processes for spent LIB recycling.

具有单价离子选择性的电驱动膜是一种很有前途的从废锂离子电池（LIB）渗滤液中可持续回收锂（Li）的技术。然而，现有的膜存在Li+选择性有限和离子渗透率低的问题。在这项研究中，开发了一种沸石咪唑盐框架（ZIF）包埋的水凝胶电驱动膜，用于电渗析（ED）选择性提取Li+。在凯夫拉芳纶纳米纤维（KANFs）的水凝胶基质中原位构建了聚二甲基二烯丙基氯化铵（PDDA）网络螺纹ZIF （QZIF）层，在磺化聚砜（SPSF）衬底上形成了稳定的复合层。得益于粒径筛分和静电斥力的协同作用，所得QZIF@KANF#SPSF膜具有快速的Li+传输，同时有效地排斥较大的二价离子（Ni2+， Co2+和Mn2+）。在5 mA cm−2的放电条件下，QZIF@KANF#SPSF膜在25 mM Li+、Ni2+、Co2+和Mn2+混合溶液中Li+的渗透率为0.45 mol m−2 h−1，Li+/Ni2+、Li+/Co2+和Li+/Mn2+的渗透率分别为13.8、12.2和10.5。这种将带电荷的zif嵌入水凝胶基质的策略，为在废LIB回收的高级分离过程中提高Li+的选择性和传输效率提供了一种强大且可扩展的途径。

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引用次数: 0