Journal of Membrane Science最新文献

Suppressing ammonia crossover with a zwitterionic poly(ionic liquid)-modified membrane for improved power generation in thermally regenerative batteries 用两性离子聚（离子液体）改性膜抑制氨交叉以改善热再生电池的发电性能

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-02-03 DOI: 10.1016/j.memsci.2026.125237

Yongsheng Zhang , Qinghua Zhang , Yu Shi , Liang Zhang , Jun Li , Xun Zhu , Qiang Liao

Thermally regenerative batteries (TRBs) present a promising route for converting low-grade waste heat into electricity. However, their practical application is limited by ammonia crossover through anion exchange membranes (AEMs), which compromises both battery performance and operational stability. To address this challenge, we developed, for the first time, a zwitterionic poly(ionic liquid)-modified AEM (ZIL-AEM) via a surface coating and in situ polymerization approach. Benefiting from the synergistic effects of physical barrier and hydrogen bonding interactions, ZIL-AEM exhibited significantly reduced ammonia permeability (4.96 × 10⁻¹⁰ cm² s⁻¹), representing a 74% decrease compared to the pristine AEM. Electrochemical analyses and visualization experiments confirmed the effectiveness of the zwitterionic coating in suppressing ammonia crossover. As a result, the ZIL-AEM delivered a maximum power density of 30.2 W m⁻² with a capacity retention of 75.5%, markedly higher than the 41.9% observed with the original membrane. Notably, the TRBs performance remained stable even at elevated ammonia concentrations. Further enhancement was achieved with a double-sided coating configuration, which strengthened the ammonia anchoring effect. These results highlight zwitterionic poly(ionic liquid)-modified membranes as a viable strategy to enhance the performance and durability of TRBs.

热再生电池（TRBs）是一种很有前途的将低品位废热转化为电能的途径。然而，它们的实际应用受到氨通过阴离子交换膜（AEMs）交叉的限制，这会损害电池的性能和操作稳定性。为了解决这一挑战，我们首次通过表面涂层和原位聚合方法开发了两性离子聚（离子液体）改性AEM （ZIL-AEM）。得益于物理屏障和氢键相互作用的协同作用，ZIL-AEM的氨渗透率显著降低（4.96 × 10−10 cm2 s−1），比原始AEM降低了74%。电化学分析和可视化实验证实了两性离子涂层抑制氨交叉的有效性。结果表明，ZIL-AEM的最大功率密度为30.2 W m−2，容量保留率为75.5%，明显高于原膜的41.9%。值得注意的是，即使在氨浓度升高的情况下，TRBs的性能仍保持稳定。双面涂层结构进一步增强了氨锚定效果。这些结果表明两性离子聚（离子液体）改性膜是提高trb性能和耐久性的可行策略。

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引用次数: 0

Cationically branched starch-based flocculants for synergistic flocculation-ultrafiltration treatment of dye wastewaters: Performance enhancement and efficient membrane fouling mitigation 阳离子支链淀粉基絮凝剂协同絮凝-超滤处理染料废水：性能增强和有效的膜污染缓解

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-02-02 DOI: 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.

染料废水具有较高的生态毒性，具有严重的环境风险；然而，传统的絮凝和超滤技术往往存在染料去除率有限和膜污染严重的问题。本研究通过线性阳离子淀粉（CS）与环氧氯丙烷轻微交联，简单合成了一种具有阳离子支链结构的新型淀粉基絮凝剂CS- ech。采用CS-ECH超滤预处理技术去除水中典型合成染料AG25。与聚合氯化铝及其线性前驱体相比，优化后的CS-ECH具有较好的絮凝效果，有效投加量范围宽（30.0 ~ 80.0 mg/L），去除率高（99.24%）。其阳离子支链结构具有松散的网状结构，增强了桥接和清扫作用，促进了大而松散的絮凝体的形成，从而提高了除染效率，并有效地中和了电荷。通过分子动力学模拟计算得到的相互作用能和配位数表明，由于CS- ech的结构不同，CS- ech与AG25的相互作用更强，捕获的AG25也比CS多。随后的超滤实现了完全脱色，使通量下降最小，稳态归一化通量为0.62，并且由于CS-ECH之前形成了多孔且易于分离的饼层，分别减轻了34.2%和85.3%的可逆和不可逆污染。絮凝-超滤组合对各种模拟染料废水和实际染料废水也表现出优异的膜可重复使用性和适应性。综上所述，CS-ECH是一种低成本、环保、高效的絮凝剂，在絮凝-超滤一体化系统中具有显著的应用潜力。

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引用次数: 0

Amplified Turing structures of covalent organic frameworks for ionic nanofiltration under extremely low pressures 极低压下用于离子纳滤的共价有机框架的放大图灵结构

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-02-02 DOI: 10.1016/j.memsci.2026.125231

Zhenshu Si , Ming Liu , Zhe Zhang , Tong Ju , Qinghua Liu , Wei Luo , Congcong Yin , Mingjie Wei , Jun Huang , Yong Wang

Turing-structured covalent organic framework (COF) membranes featuring ordered nanopores and internal cavities are appealing for high-efficient ionic nanofiltration, while the efficient and controllable preparation remains challenging. Herein, we report Turing-structured COF membranes with amplified inner cavities for fast and selective ion sieving. A modulation layer is constructed that allows catalyst and water to transport from the inner pores to the reaction zone, triggering local activation via rapid COF formation. The as-formed COF sheets further obstruct the diffusion of reactants, enabling long-range inhibition to meet the essential for Turing structures. An unexplored Turing structure with seamlessly bridged nanobowls and amplified inner cavities are created, delivering exceptional separation performances that can be operated under extremely low pressures. The resulting membrane exhibits 6-fold enhancement on methanol permeation compared to the non-Turing membrane, and high selectivity for rare metal ions of up to 75.5 (Cs⁺/La³⁺). This work provides a pathway to unlock the potential of Turing-structured COF membranes for various task-specific separations.

具有有序纳米孔和内腔的图灵结构共价有机框架（COF）膜是高效离子纳滤的理想选择，但高效可控的制备仍是一个挑战。在此，我们报道了具有放大内腔的图灵结构COF膜，用于快速和选择性离子筛选。构建了一个调制层，允许催化剂和水从内部孔隙运输到反应区，通过快速的COF形成触发局部活化。形成的COF片进一步阻碍了反应物的扩散，实现了长距离抑制，满足了图灵结构的要求。一种未开发的图灵结构，具有无缝桥接的纳米碗和放大的内腔，可以在极低的压力下运行，提供卓越的分离性能。与非图灵膜相比，该膜对甲醇的渗透性提高了6倍，对稀有金属离子的选择性高达75.5 （Cs+/La3+）。这项工作为解锁图灵结构COF膜用于各种特定任务分离的潜力提供了一条途径。

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引用次数: 0

Unveiling mitigation mechanism of multi-dimension fouling of suspended photocatalytic-membrane reactor for advanced treatment of secondary effluent 揭示悬浮光催化膜反应器深度处理二级出水多维污染的缓解机理

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-31 DOI: 10.1016/j.memsci.2026.125221

Tianyang Wang, Zhiwei Zhou, Shenbin Cao, Xing Li, Yuantian Zhao, Nan Wang, Jiawei Ren

Ultrafiltration membrane fouling remains a critical constraint on the long-term operation of suspended photocatalytic-membrane reactor (SPMR). Herein, an integrated SPMR comprising a photocatalytic zone, a catalyst separation/reflux zone, and an ultrafiltration zone was developed. During 32 days of cumulative effective operation (catalyst dosage of 1 g/L, membrane flux of 20 LMH, light power density of 4.58 mW/cm²), the membrane fouling mitigation efficacy and underlying mechanisms of SPMR during the treatment of effluent organic matter (EfOM) were investigated, with particular focus on the influence of EfOM transformation properties, catalyst deposition on the membrane, and microbial proliferation. Results indicated that SPMRs achieved average removal efficiencies exceeding 57% for UV₂₅₄ and 21% for DOC, with photocatalytic process primarily responsible for degrading protein-like and humic-like fluorescent substances, and organic fractions with molecular weights <1000 Da. Photocatalysis disrupted the aromatic structure of EfOM, reduced ultrafiltration fouling load, and simultaneously suppressed cake layer microbial activity, leading to decreased microbial community richness and diversity, and weakened interspecific cooperation. The synergistic action of these mechanisms reduced EPS content in the cake layer while increasing the protein-to-polysaccharide ratio, resulting in a thinner and more porous cake layer configuration. These transformations were accompanied by a reduction in polar functional groups such as –CO and amide groups, which collectively diminished foulant adhesion propensity and self-aggregation tendency. Consequently, the reversible fouling resistance in the SPMRs were reduced by exceeding 65.0% compared to direct ultrafiltration. Meanwhile, BTP particles (d₅₀ = 45.7 μm), with sizes substantially larger than ultrafiltration membrane pores, formed a high-porosity deposition layer without exacerbating membrane fouling. These findings elucidate the fouling mitigation mechanisms in continuously operated SPMRs and underscore their potential significance for advanced treatment of secondary effluent.

超滤膜污染是制约悬浮式光催化膜反应器长期运行的重要因素。在此，开发了一个集成的SPMR，包括光催化区、催化剂分离/回流区和超滤区。在32天的累积有效运行（催化剂用量为1 g/L，膜通量为20 LMH，光功率密度为4.58 mW/cm2）中，研究了SPMR在处理出水有机物（EfOM）过程中的膜污染缓解效果和潜在机制，重点研究了EfOM转化特性、催化剂沉积在膜上和微生物增殖的影响。结果表明，SPMRs对UV254的平均去除率超过57%，对DOC的平均去除率超过21%，光催化过程主要负责降解蛋白质类和腐殖质类荧光物质，以及分子量为1000 Da的有机组分。光催化破坏了EfOM的芳香结构，降低了超滤污染负荷，同时抑制了饼层微生物活性，导致微生物群落丰富度和多样性下降，种间合作减弱。这些机制的协同作用降低了饼层中EPS的含量，同时增加了蛋白与多糖的比例，使饼层结构更薄、更多孔。这些转变伴随着极性官能团（如-CO和酰胺基团）的减少，这些官能团共同减少了污染物的粘附倾向和自聚集倾向。结果表明，与直接超滤相比，SPMRs的可逆阻垢率降低了65.0%以上。BTP颗粒（d50 = 45.7 μm）粒径大大大于超滤膜孔，形成了高孔隙度的沉积层，但并未加重膜污染。这些发现阐明了连续运行SPMRs的污染缓解机制，并强调了它们对二级废水深度处理的潜在意义。

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引用次数: 0

Transition state theory unveils enthalpy–entropy interplay in polyamide nanocomposite membranes for enhanced water–salt selectivity 过渡态理论揭示了聚酰胺纳米复合膜中增强水盐选择性的焓熵相互作用

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-29 DOI: 10.1016/j.memsci.2026.125222

Jiujing Xu , Cheng Chen , Rukang Jiang , Bisheng Li , Leihong Zhao , Liguo Shen , Hongjun Lin

Polyamide nanocomposite membranes are promising for seawater desalination, yet the molecular mechanisms governing water and solute transport remain unclear. Here, we synthesized a conjugated microporous polymer (IPA–PPA) and embedded it within the interlayer of polyamide thin-film nanocomposite (CMP–TFN) membranes. Using transition state theory and the Eyring equation, we deconvoluted intrinsic water and ion permeability into enthalpic and entropic contributions to probe the molecular basis of water–salt selectivity. The partially protruding, intrinsically microporous IPA–PPA generated additional nanoscale transport channels and modified polyamide morphology and surface charge, thereby lowering mass-transfer resistance. As a result, CMP–TFN membranes achieved high Na₂SO₄ rejection (98.4 %) alongside enhanced water flux, antifouling performance, and long-term stability. Transition state analysis revealed that increased water transport was driven by higher activation entropy (ΔS^‡), whereas stronger solute rejection correlated with elevated activation enthalpy (ΔH^‡). The synergy between enlarged pore structures (increasing ΔS^‡) and stronger surface charge (increasing ΔH^‡) collectively modulated ion transport, ultimately improving water–salt selectivity. Our findings demonstrate that enthalpy–entropy interplay underpins water–ion discrimination in polyamide nanocomposite membranes, enabling high selectivity.

聚酰胺纳米复合膜在海水淡化领域具有广阔的应用前景，但其控制水和溶质运输的分子机制尚不清楚。在这里，我们合成了一种共轭微孔聚合物（IPA-PPA），并将其嵌入聚酰胺薄膜纳米复合材料（CMP-TFN）膜的中间层中。利用过渡态理论和Eyring方程，我们将水和离子的固有渗透性解卷积为焓和熵贡献，以探讨水盐选择性的分子基础。部分突出的微孔IPA-PPA产生了额外的纳米级传输通道，并修饰了聚酰胺的形态和表面电荷，从而降低了传质阻力。结果，CMP-TFN膜获得了高Na2SO4截留率（98.4%），同时增强了水通量、防污性能和长期稳定性。过渡态分析显示，更高的活化熵（ΔS‡）驱动了水输运的增加，而更强的溶质排斥与升高的活化焓相关（ΔH‡）。扩大的孔隙结构（增加ΔS‡）和更强的表面电荷（增加ΔH‡）之间的协同作用共同调节离子传输，最终提高水盐选择性。我们的研究结果表明，在聚酰胺纳米复合膜中，焓熵相互作用是水离子鉴别的基础，从而实现了高选择性。

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引用次数: 0

Synergistic rigid-flexible COF-based composite membranes for enhanced proton conductivity and mechanical strength 增强质子导电性和机械强度的刚柔复合膜

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-29 DOI: 10.1016/j.memsci.2026.125213

Shiyi Zhu , Liufei Wei , Xu Dong , Zhong Gao , Minghao Zhou , Jiaojiao Cao , Zitian Zhou , Hong Wu , Zhongyi Jiang

The advancement of electrochemical energy conversion technologies calls for proton exchange membrane (PEM) that integrates excellent proton conductivity with robust mechanical performance. Herein, we present a synergistic rigid-flexible approach to achieving simultaneous enhancement of these two properties by combining covalent organic framework (COF) nanosheets (TpPa-SO₃H) with a sulfonated polyvinyl alcohol (SPVA) polymer, where the TpPa-SO₃H nanosheets serve as the rigid scaffold and SPVA acts as the flexible gap-filling agent within the interlayers of the rigid nanosheets. Benefiting from the precisely positioned proton sites (-SO₃H) on the COF nanosheets and the abundant proton carriers and hydrogen-bond network (-SO₃H and -OH) in the intercalated SPVA, the resulting PEM exhibits exceptional proton conductivity. Moreover, the hydrogen bonding interaction and physical entanglement between COF nanosheets and SPVA enable the significantly strengthened mechanical performance. The optimal TpPa-SO₃H/SPVA composite PEM demonstrates an outstanding proton conductivity of 945.7 mS cm^-1 (80 °C, 98 % RH) and enhanced mechanical strength of 115.0 MPa. As a result, the TpPa-SO₃H/SPVA PEM shows enhanced electrochemical hydrogen compression (831 kPa) and fuel cell performance (525.6 mW/cm^-2). This work develops a rigid-flexible coupled PEM with high proton conductivity and mechanical strength, advancing diverse electrochemical energy conversion technologies.

电化学能量转换技术的进步要求质子交换膜（PEM）具有优异的质子导电性和强大的机械性能。在此，我们提出了一种刚柔协同的方法，通过将共价有机框架（COF）纳米片（TpPa-SO3H）与磺化聚乙烯醇（SPVA）聚合物结合来实现这两种性能的同时增强，其中TpPa-SO3H纳米片作为刚性支架，SPVA作为刚性纳米片中间层中的柔性间隙填充剂。得益于COF纳米片上精确定位的质子位点（-SO3H）和插层SPVA中丰富的质子载体和氢键网络（-SO3H和-OH），生成的PEM具有优异的质子导电性。此外，COF纳米片与SPVA之间的氢键相互作用和物理纠缠使COF纳米片的力学性能得到了显著增强。最佳的TpPa-SO3H/SPVA复合PEM在80°C， 98% RH条件下的质子电导率为945.7 mS cm-1，机械强度提高至115.0 MPa。结果表明，TpPa-SO3H/SPVA PEM的电化学氢压缩性能（831 kPa）和燃料电池性能（525.6 mW/cm-2）均有所提高。本研究开发了一种具有高质子导电性和机械强度的刚柔耦合PEM，推动了多种电化学能量转换技术的发展。

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引用次数: 0

Silicon-tailored carbon molecular sieve membranes enable precise and stable hydrogen separation 硅定制碳分子筛膜实现精确和稳定的氢分离

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-28 DOI: 10.1016/j.memsci.2026.125220

Chuning Fang , Xingyu Chen , Zhinan Fu , Zuoxiang Zeng , Linfeng Lei , Zhi Xu

The requirement for efficient CO₂ capture during hydrogen production from fossil fuels promotes the development of advanced, energy-efficient solutions, while the application of temperature/pressure-resistant membranes is a promising candidate. Polymer-derived carbon molecular sieve (CMS) membranes with precise molecular discrimination capability hold attractive promise in H₂/CO₂ separation. Nonetheless, microstructure tuning for the precise discrimination of H₂ and CO₂ has so far remained challenging, and physical aging is also an inevitable problem. Herein, we proposed a precursor-crosslinked strategy via chemical functionalization of cellulose precursor to enhance molecular sieving ability and simultaneously overcome physical aging of the derived CMS membranes. The membrane presents a remarkable H₂/CO₂ selectivity of 91.0 and shows only 14 % H₂ permeance loss in 120 days. Besides, it maintains excellent separation performance over 300 h under high pressure (up to 20 bar) and high temperature of 140 °C with a feeding of 50 mol% H₂/50 mol% CO₂. This study provides an effective way to construct the sub-nano-sized microporous structure of CMS membranes and demonstrates its potential for blue hydrogen purification under harsh conditions.

化石燃料制氢过程中对高效二氧化碳捕获的需求促进了先进、节能解决方案的发展，而耐温/耐压膜的应用是一个很有前途的候选者。聚合物衍生碳分子筛（CMS）膜具有精确的分子识别能力，在H2/CO2分离中具有广阔的应用前景。然而，精确区分H2和CO2的微观结构调整至今仍然具有挑战性，物理老化也是不可避免的问题。在此，我们提出了一种前体交联策略，通过纤维素前体的化学功能化来提高分子筛选能力，同时克服衍生的CMS膜的物理老化。该膜的H2/CO2选择性为91.0，在120天内仅损失14%的H2透性。此外，在高压（高达20 bar）和高温（140°C）下，在进料为50 mol% H2/50 mol% CO2的条件下，它在300 h内保持了优异的分离性能。本研究为构建亚纳米级CMS膜微孔结构提供了有效途径，并展示了其在恶劣条件下净化蓝氢的潜力。

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引用次数: 0

Covalently bonded nanofiltration membranes with enhanced interlayer stability and back-flush resistance 具有增强层间稳定性和抗反冲性的共价键纳滤膜

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-27 DOI: 10.1016/j.memsci.2026.125211

Xiyue Cai , Yonggang Li , Zejin Yu , Yingjie Fu , Jing Guo , Lei Dai , Yaohan Chen , Shenghai Li , Suobo Zhang

Nanofiltration (NF) membrane represents an environmental-friendly and easy-to-operate water purification technology. However, NF membranes inevitably suffer from fouling, resulting in significant deterioration of separation performance and shortened operational lifespan. The polyamide (PA) separating layer of commercial thin film composite nanofiltration (TFC-NF) membranes is typically fabricated via interfacial polymerization (IP) on supporting membrane. The interfacial adhesion between the PA layer and the supporting membrane is primarily governed by weak van der Waals interactions, rendering the PA layer susceptible to be damaged during operation and recycling. In this work, we synthesized and employed a carboxyl-functionalized polymer (PEAK-COOH) as the supporting membrane material. Through a one-step phase inversion-surface amination process conducted in an aqueous piperazine (PIP) solution, coupled with in-situ IP process, we successfully fabricated a TFC NF membrane (PEAK–COOH–NF) in which the separating layer and the supporting membrane were robustly integrated through extensive covalent bonds. The separation layer fabricated with such strong interfacial bonding remained intact even under a maximum normal load of 0.15 mN in nano-scratch test, whereas the commercial NF270 membrane and TFC-NF membrane prepared on polyethersulfone (PES) supporting membrane exhibited structural failure at only 0.065 mN and 0.073 mN, respectively. This excellent interlayer adhesion enables the membrane to withstand back-flushing cleaning treatment at pressures up to 0.9 MPa without exhibiting significant performance deterioration, with its rejection remaining at 98.60 % after back-flushing. Finite element simulations further elucidate how this robust covalent interfacial bonding enhances the overall structural stability of the membrane. Furthermore, PEAK–COOH–NF exhibited a higher Na₂SO₄ rejection than NF270 due to the high cross-linking degree with 94.12 %. This study not only introduces a continuous fabrication strategy that enables TFC-NF membranes with exceptionally strong interfacial bonding, but also provides both methodological insights and a robust material platform to support effective back-flush operations in practical nanofiltration applications.

纳滤（NF）膜是一种环境友好、易于操作的水净化技术。然而，纳滤膜不可避免地会受到污染，导致分离性能显著下降，使用寿命缩短。商用薄膜复合纳滤（TFC-NF）膜的聚酰胺（PA）分离层通常是在支撑膜上通过界面聚合（IP）制备的。聚苯乙烯层与支撑膜之间的界面粘附主要受弱范德华相互作用的支配，使得聚苯乙烯层在操作和回收过程中容易被破坏。在这项工作中，我们合成并使用了一种羧基功能化聚合物（PEAK-COOH）作为支撑膜材料。通过在哌嗪（PIP）水溶液中进行的一步相反表面胺化工艺，结合原位IP工艺，成功制备了一种分离层和支撑膜通过广泛的共价键牢固结合的TFC NF膜（峰cooh - NF）。在纳米划伤测试中，即使在0.15 mN的最大正常载荷下，具有如此强界面键合的分离层仍然保持完整，而在聚醚砜（PES）支撑膜上制备的商用NF270膜和TFC-NF膜分别在0.065 mN和0.073 mN下出现结构破坏。这种优异的层间附着力使膜能够承受高达0.9 MPa压力下的反冲洗清洗处理，而不会表现出明显的性能下降，反冲洗后的去除率仍为98.60%。有限元模拟进一步阐明了这种强大的共价界面键如何增强膜的整体结构稳定性。此外，由于交联度高，PEAK-COOH-NF的Na2SO4截留率高于NF270（94.12%）。这项研究不仅介绍了一种连续制造策略，使TFC-NF膜具有异常强大的界面键合，而且还提供了方法论见解和强大的材料平台，以支持实际纳滤应用中有效的反冲洗操作。

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引用次数: 0

Construction of TpPa-COF interlayered positive nanofiltration membrane for efficient removal of high-concentration heavy metal ions 高效去除高浓度重金属离子的TpPa-COF层间正纳滤膜的构建

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-27 DOI: 10.1016/j.memsci.2026.125209

Houyi Peng, Wenqi Zhang, Ji Chen, Qi Zhang, Xiao Xiao, Weixing Li

Polyamide nanofiltration membranes often exhibit reduced rejection rates and flux decline under high ionic strength conditions. In order to efficiently remove heavy metal ions (HMIs) from water, a TpPa-COF interlayered positive nanofiltration membrane was proposed. TpPa-1 COF was synthesized and then reacted with 1,3,5-Benzenetricarbonyl trichloride (TMC) to narrow the pore size. The narrowed pore size from 18 Å to 5.4 Å was designed for rejection of heavy metal ions (>5.8 Å). Then, the membrane was functionalized with polyethyleneimine (PEI) grafting to impart positive surface charges for enhanced HMIs removal. The developed membrane was systematically characterized and evaluated for its physicochemical properties and performance through attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cold-field emission scanning electron microscope (SEM), and atomic force microscopy (AFM). The fabricated membrane achieved exceptional rejections of Cr³⁺ (99.04 %), Mn²⁺ (97.03 %), Co²⁺ (97.74 %), Ni²⁺ (98.43 %), Zn²⁺ (98.85 %), and Cd²⁺ (99.07 %) at a feed concentration of 1000 ppm. Notably, the membrane maintained the rejection efficiency of 90 % under a higher feed concentration of 6000 ppm, which is better than the commercial NF3 membrane. After 7 days of continuous operation, the rejection of HMIs exceeded 98.4 %, demonstrating the great stability. When treating actual electroplating wastewater, the membrane showed good performance. The removal rate for major ions (Cr(VI), Co²⁺, Cu²⁺, Mn²⁺, Ni²⁺, Zn²⁺) reached from 97.4 % to 99.99 %. The developed membrane exhibited better performance than commercial membrane, demonstrating the practical potential in treating actual wastewater.

在高离子强度条件下，聚酰胺纳滤膜往往表现出较低的截留率和通量下降。为了高效去除水中重金属离子，提出了一种TpPa-COF层间正纳滤膜。合成了tpa -1 - COF，并与1,3,5-苯三羰基三氯化物（TMC）反应以缩小孔径。孔径从18 Å缩小到5.4 Å是为了去除重金属离子而设计的（>5.8 Å）。然后，用聚乙烯亚胺（PEI）接枝对膜进行功能化，赋予表面正电荷以增强hmi的去除。通过衰减全反射傅里叶变换红外光谱（ATR-FTIR）、x射线衍射（XRD）、x射线光电子能谱（XPS）、冷场发射扫描电镜（SEM）和原子力显微镜（AFM）对制备的膜进行了系统的表征和理化性能评价。在1000ppm的投加浓度下，制备的膜对Cr3+(99.04%)、Mn2+(97.03%)、Co2+(97.74%)、Ni2+(98.43%)、Zn2+(98.85%)和Cd2+(99.07%)的去除率达到了很高的水平。值得注意的是，在较高的进料浓度为6000 ppm的情况下，膜的截留效率保持在90%以上，优于工业生产的NF3膜。连续运行7 d后，hmi的排异率超过98.4%，具有较好的稳定性。在实际电镀废水处理中，该膜表现出良好的性能。对主要离子（Cr（VI）、Co2+、Cu2+、Mn2+、Ni2+、Zn2+）的去除率达到97.4% ~ 99.99%。该膜的性能优于工业膜，在实际废水处理中具有一定的应用潜力。

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引用次数: 0

A Janus nanofiltration membrane synergistically constructed by a CNC–COOH interlayer and crown–ether channels for high-efficiency lithium extraction 以CNC-COOH夹层和冠醚通道协同构建的Janus纳滤膜用于高效锂提取

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2026-01-27 DOI: 10.1016/j.memsci.2026.125208

Zhicheng Wang , Tiansheng Gao , Yuqian Yang , Zizhen Peng , Wenzhong Ma , Qiuyan Bi , Yakai Lin , Hideto Matsuyama

The increasing demand for lithium resources highlights the need for nanofiltration (NF) membranes with high permeability and selectivity for processing salt-lake brines. In this study, an ultrathin Janus NF membrane featuring Li⁺-selective nanochannels was fabricated via interfacial polymerization for Li⁺/Mg²⁺ separation. Carboxylated cellulose nanocrystals (CNC–COOH) were deposited onto a polyvinylidene fluoride (PVDF) substrate to form an interlayer, and 15-crown-5 (15-C-5) was incorporated into the polyamide (PA) layer, yielding the PVDF/CCNC–15C5-PA membrane. The CNC–COOH interlayer increased membrane hydrophilicity and surface negative charge, and synergistically interacted with 15-C-5 to enhance the interaction with polyethyleneimine, resulting in a thin, defect-free PA layer of approximately 63 nm. Meanwhile, 15-C-5 formed host–guest complexes with Li⁺, establishing Li⁺-selective nanochannels that promoted Li⁺ transport. The combined modifications yielded a PVDF/CCNC–15C5-PA membrane with a water permeance of 15.4 L m⁻² h⁻¹·bar⁻¹ and a Li⁺/Mg²⁺ separation factor of 17.8. This work presents a dual-functional design strategy that integrates interfacial engineering with molecular recognition for advanced ion-selective separation.

随着锂资源需求的不断增长，对高透性、高选择性纳滤膜的需求日益突出。本研究通过界面聚合制备了具有Li+选择性纳米通道的超薄Janus NF膜，用于Li+/Mg2+的分离。将羧化纤维素纳米晶体（CNC-COOH）沉积在聚偏氟乙烯（PVDF）衬底上形成夹层，并将15-冠-5 （15-C-5）掺入聚酰胺（PA）层，得到PVDF/ CCNC-15C5-PA膜。CNC-COOH中间层增加了膜的亲水性和表面负电荷，并与15-C-5协同作用，增强了与聚乙烯亚胺的相互作用，形成了约63 nm的薄而无缺陷的PA层。同时，15-C-5与Li+形成主客体配合物，建立Li+选择性纳米通道，促进Li+运输。复合改性后的PVDF/ cccnc - 15c5 - pa膜的透水性为15.4 L m−2 h−1·bar−1，Li+/Mg2+分离系数为17.8。这项工作提出了一种双功能设计策略，将界面工程与分子识别相结合，用于高级离子选择分离。

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引用次数: 0