Journal of Membrane Science最新文献_第6页

Fabrication of POSS-centered polyester network as high anti-chlorine and anti-fouling separation layer of membrane via successive Photo-ATRP and interfacial polymerization for molecular separation 通过连续光-ATRP 和界面聚合制造以 POSS 为中心的聚酯网络，作为膜的高抗氯和防污分离层，实现分子分离

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-22 DOI: 10.1016/j.memsci.2024.123432

Xiaoling Xu , Bin Peng , Yanqiu Wang , Yaqi Dong , Hui Wang , Wentong Chen , Yan Liu , Qiang Zhang

The incorporation of polyhedral oligomeric sesquisiloxane (POSS), a distinctive nanoparticle, into the membrane separation layer represents an effective strategy for enhancing the chlorine resistance of membranes. This modification contributes to both the durability of the membrane and its separation efficiency. However, POSS is easy to agglomerate, which affects the separation performance of the membrane. In this paper, POSS-centered polyhydroxy polymer (OMEPOSS-P(GMA-NMDG)) was synthesized via photo-induced atom transfer radical polymerization and used as water-soluble monomer to prepare polyester separation layer on porous substrates through interfacial polymerization with trimelanoyl chloride. The obtained POSS-centered polyester membrane exhibits a high dye removal rate exceeding 99 %, and it can realize the screening of dye molecules with different molecular weight and different charge. Notably, the membrane demonstrates excellent chlorine resistance, maintaining effective separation efficiency after exposure to sodium hypochlorite solutions at concentrations of 10 000 ppm for 96 h and 1000 ppm for 7 days. It is worth noting that the membrane showed high anti-fouling performance. This method provides a useful guideline for the development of chlorine-resistant and anti-fouling separation membranes.

在膜分离层中加入多面体低聚倍半硅氧烷（POSS）这种独特的纳米粒子，是提高膜耐氯性的有效策略。这种改性有助于提高膜的耐久性和分离效率。然而，POSS 容易团聚，影响膜的分离性能。本文通过光诱导原子转移自由基聚合合成了以 POSS 为中心的聚羟基聚合物（OMEPOSS-P(GMA-NMDG)），并将其作为水溶性单体，通过与三苯甲酰氯的界面聚合在多孔基底上制备聚酯分离层。所制备的以 POSS 为中心的聚酯膜对染料的去除率高达 99% 以上，并能实现对不同分子量、不同电荷的染料分子的筛选。值得注意的是，该膜具有优异的耐氯性，在浓度为 10 000 ppm 的次氯酸钠溶液中暴露 96 小时和 1000 ppm 的次氯酸钠溶液中暴露 7 天后，仍能保持有效的分离效率。值得注意的是，这种膜还具有很高的防污性能。该方法为开发抗氯防污分离膜提供了有用的指导。

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引用次数: 0

Engineering the ultrathin polyamide nanofilm featuring high free volume via interfacial polymerization for efficient CO2 capture 通过界面聚合技术制造具有高自由体积的超薄聚酰胺纳米薄膜，用于高效捕获二氧化碳

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-22 DOI: 10.1016/j.memsci.2024.123443

Fei Shi , Qinghua Li , Ye Yuan , Yi Yang , Xingzhong Cao , Menglong Sheng , Song Zhao , Zhi Wang

Interfacial polymerization (IP) has been received as an indispensable technology to fabricate thin-film composite (TFC) membranes for gas separation because of the simple and designable process. However, achieving the highly permeable polyamide (PA) TFC membrane for CO₂ capture via the IP technique remains challenging. Herein, a highly CO₂-permeable PA TFC membrane was synthesized by the polycondensation of N, N-Bis [3-(methylamino) propyl]methylamine (BMAPAm) and trimesoyl chloride (TMC). The ultrathin (∼47 nm) PA TFC membrane featuring with high free volume exhibited excellent CO₂ permeance with moderate CO₂/N₂ selectivity. The causes of this desired structure were systematically investigated from the aspects of monomer supply and molecular structure, in which the 3,3′-diamino-N-methyldipropylamine (DNMDAm) was used as a comparison. The results illustrated the underlying monomer-structure-performance relationships of IP-made membranes, demonstrating the solid potential of the IP technology specifically toward high-performance CO₂ capture membranes. Finally, a pilot-scale continuous membrane fabrication process was demonstrated.

界面聚合（IP）因其工艺简单、可设计性强，已被视为制造气体分离薄膜复合（TFC）膜不可或缺的技术。然而，通过 IP 技术实现用于二氧化碳捕集的高渗透性聚酰胺（PA）TFC 膜仍然具有挑战性。本文通过 N，N-双[3-（甲基氨基）丙基]甲胺（BMAPAm）和三甲基甲酰氯（TMC）的缩聚合成了高二氧化碳渗透性聚酰胺 TFC 膜。具有高自由体积的超薄（∼47 nm）PA TFC 膜表现出优异的 CO2 渗透性和适度的 CO2/N2 选择性。研究人员以 3,3′-二氨基-N-甲基二丙胺（DNMDAm）为比较对象，从单体供应和分子结构两方面系统地研究了这种理想结构的成因。结果表明了 IP 制造膜的基本单体-结构-性能关系，证明了 IP 技术在高性能二氧化碳捕集膜方面的巨大潜力。最后，还展示了中试规模的连续膜制造工艺。

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引用次数: 0

Impregnation, dehydration and crosslinking of responsive organoboron polymer to generate smart gating membrane for multimolecular gradient separation 浸渍、脱水和交联反应性有机硼聚合物，生成用于多分子梯度分离的智能门控膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-22 DOI: 10.1016/j.memsci.2024.123440

Xinzhao Luo , Yaqi Dong , Liyuan Fan , Mengyao Zhao , Qian Wang , Haisheng Zhang , Qiang Zhang

Responsive materials have garnered increasing attention in the membrane separation field. However, fabricating smart gating membranes with tunable pore sizes to separate complex systems remains challenging. Herein, gating membranes with boroxine skeleton and temperature-tunable pores were successfully fabricated by fixing lower critical solution temperature (LCST)-type organoboron polymers (poly(N-isopropylacrylamide-co-glycidyl methacrylate/3-aminophenylboronic acid), PNG-APBA) onto the membrane surface via "impregnation-dehydration-crosslinking" strategy. The conformational behavior of the NIPAM-containing polymer chains (shrinking above LCST-stretching below LCST) serves as a functional gate, enabling the membranes to achieve reversibly tunable pore sizes and surface properties. The modified membranes exhibit gradient separation capabilities for small/medium/large molecules in complex polymer systems through temperature-tunable channels. The tunable pores also provided a potential tool for the high-selectivity separation of mixed proteins, such as lysozyme (LZM) and hemoglobin (Hb). Notably, the conformational behavior of the polymer chains endowed the membranes with excellent self-cleaning ability (FRR> 99.5 %), while the boroxine network enhanced the grafting stability of the polymer chains, ensuring effective reversibility and repeatability of membranes.

响应材料在膜分离领域受到越来越多的关注。然而，制造具有可调孔径的智能选通膜以分离复杂系统仍具有挑战性。本文通过 "浸渍-脱水-交联 "策略，将低临界溶液温度（LCST）型有机硼聚合物（聚（N-异丙基丙烯酰胺-共缩水甘油基甲基丙烯酸酯/3-氨基苯基硼酸，PNG-APBA）固定在膜表面，成功制备了具有硼氧骨架和温度可调孔隙的选通膜。含有 NIPAM 的聚合物链的构象行为（高于 LCST 时收缩，低于 LCST 时拉伸）可作为功能门，使膜实现可逆的孔径大小和表面特性。改性膜通过温度可调的通道，在复杂的聚合物体系中实现了小分子/中分子/大分子的梯度分离能力。可调孔还为溶菌酶（LZM）和血红蛋白（Hb）等混合蛋白质的高选择性分离提供了一种潜在工具。值得注意的是，聚合物链的构象行为赋予了膜出色的自清洁能力（FRR> 99.5 %），而硼氧网络增强了聚合物链的接枝稳定性，确保了膜的有效可逆性和可重复性。

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引用次数: 0

Elucidating organic and nutrient transport mechanisms in polyelectrolyte modified membranes for selective nutrient recovery 阐明用于选择性养分回收的聚电解质改性膜中的有机物和养分输送机制

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-21 DOI: 10.1016/j.memsci.2024.123438

Km Prottoy Shariar Piash , Noah Sprouse , Cole Hodges , Lian-Shin Lin , Oishi Sanyal

This work focuses on understanding and analyzing the transport mechanisms of organics and nutrient ions (NH₄⁺, K⁺) through polyelectrolyte-based membranes, aimed at the selective recovery of nutrients from nutrient-rich resources such as anaerobic digestate. In this study, commercial nanofiltration (NF) membranes were modified by the layer-by-layer (LbL) deposition of oppositely charged polyelectrolytes, utilizing a wide range of parameters such as polyelectrolyte type, deposition pH, salt (NaCl) concentration, polymer cross-linking, etc. Such modifications resulted in membranes exhibiting characteristics that indicate a trade-off relationship between nutrient passage and nutrients/organics selectivity. Our findings suggest that nutrient passage is primarily facilitated by surface charge, while size-exclusion plays a vital role in retaining the organics. Ionically crosslinked polyelectrolyte multilayer (PEM) membranes exhibit superior nutrient passage (up to ∼30 % higher) compared to commercial NF membranes, while covalently crosslinked PEM membranes achieve higher (∼12 % higher) organics rejection. In addition, membranes with such covalent crosslinking exhibit intra-nutrient (NH₄⁺/K⁺) selectivity of ∼1.8, when tested with binary NH₄⁺/K⁺ mixtures – a rather surprising membrane property, since both ions have similar hydrated radii. This study provides a fundamental framework of membrane design for selectively recovering nutrients from a variety of nutrient-rich sources.

这项工作的重点是了解和分析有机物和营养离子（NH4+、K+）通过基于聚电解质的膜的传输机制，目的是从富含营养物质的资源（如厌氧沼渣）中选择性地回收营养物质。在这项研究中，通过逐层（LbL）沉积带相反电荷的聚电解质对商用纳滤膜进行了改性，利用了多种参数，如聚电解质类型、沉积 pH 值、盐（NaCl）浓度、聚合物交联等。这种改性使膜表现出的特性表明，营养物质通过率与营养物质/有机物选择性之间存在权衡关系。我们的研究结果表明，营养物质的通过主要是由表面电荷促进的，而尺寸排阻在保留有机物方面起着至关重要的作用。与商业 NF 膜相比，离子交联聚电解质多层膜（PEM）的营养物通过率更高（高出 30%），而共价交联 PEM 膜的有机物去除率更高（高出 12%）。此外，当使用二元 NH4+/K+ 混合物进行测试时，具有这种共价交联的膜表现出营养物（NH4+/K+）内选择性∼1.8--这是一种相当令人惊讶的膜特性，因为这两种离子具有相似的水合半径。这项研究为从各种富含营养物质的来源中选择性回收营养物质的膜设计提供了一个基本框架。

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引用次数: 0

Polyamide membranes with tannic acid-ZIF-8 for highly permeable and selective ion-ion separation 含有单宁酸-ZIF-8 的聚酰胺膜，用于高渗透性和选择性离子-离子分离

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-20 DOI: 10.1016/j.memsci.2024.123435

Xing Lai , Hongxiang Zhang , Weiye Xu , Jian You , Huaiyin Chen , Yongzhao Li , Weihe Yu , Jianying Huang , Changfa Xiao , Yuekun Lai , Weilong Cai

Highly permeable polyamide (PA) membranes with precise ion selection can be used for many energy-efficient chemical separations but are limited by membrane inefficiencies. Herein, polyphenol-mediated ZIF-8 nanoparticles with hydroxyl-rich hollow structure were synthesized by tannic acid tailored regulation. PA-based membranes with fast penetration, high retention, and precise Cl⁻/SO₄²⁻ selection were then synthesized through spatially and temporally controlling interfacial polymerization with modified ZIF-8 nanoparticles (tZIF-8) as aqueous phase additives or as interlayers. The effects of the embedding position of tZIF-8 on the structure, morphology, physicochemical properties, and performance of PA-based membranes were explored through a sequence of characterization techniques. The results revealed that the PA-based membrane with tZIF-8 embedded in the PA layer could achieve a high water permeance of 24.8 L m⁻² h⁻¹ bar⁻¹ with a high retention of 99.4 % Na₂SO₄ and a Cl⁻/SO₄²⁻ selectivity of 141, which was superior to most state-of-the-art PA-based membranes. Comparatively, the Cl⁻/SO₄²⁻ selection of the PA-based membrane with tZIF-8 embedded between the PA layer and the substrate was 136, while the water permeance was slightly enhanced to 28.2 L m⁻² h⁻¹ bar⁻¹. Excitingly, the resulting membranes all exhibit superior antifouling properties and stability. Our facile strategy for tuning membrane microstructures provides new ideals into the development of highly permeable and excellently selective PA-based membranes for precise ion sieving.

具有精确离子选择能力的高渗透性聚酰胺（PA）膜可用于多种高能效化学分离，但受限于膜的低效性。本文通过单宁酸定制调节合成了多酚介导的富羟基中空结构 ZIF-8 纳米颗粒。然后，通过空间和时间控制界面聚合，以改性 ZIF-8 纳米颗粒（tZIF-8）作为水相添加剂或夹层，合成了具有快速渗透、高截留和精确 Cl-/SO42- 选择的 PA 基膜。通过一系列表征技术探讨了 tZIF-8 嵌入位置对 PA 基膜的结构、形态、理化性质和性能的影响。结果表明，在 PA 层中嵌入 tZIF-8 的 PA 基膜的透水率高达 24.8 L m-2 h-1 bar-1，Na2SO4 的截留率高达 99.4 %，Cl-/SO42- 的选择性为 141，优于大多数最先进的 PA 基膜。相比之下，在 PA 层和基底之间嵌入 tZIF-8 的 PA 基膜的 Cl-/SO42- 选择性为 136，而透水性则略有提高，达到 28.2 L m-2 h-1 bar-1。令人兴奋的是，所制备的膜均表现出卓越的防污性能和稳定性。我们调整膜微结构的简便策略为开发用于精确离子筛分的高渗透性和高选择性聚酰胺基膜提供了新的思路。

{"title":"Polyamide membranes with tannic acid-ZIF-8 for highly permeable and selective ion-ion separation","authors":"Xing Lai , Hongxiang Zhang , Weiye Xu , Jian You , Huaiyin Chen , Yongzhao Li , Weihe Yu , Jianying Huang , Changfa Xiao , Yuekun Lai , Weilong Cai","doi":"10.1016/j.memsci.2024.123435","DOIUrl":"10.1016/j.memsci.2024.123435","url":null,"abstract":"<div><div>Highly permeable polyamide (PA) membranes with precise ion selection can be used for many energy-efficient chemical separations but are limited by membrane inefficiencies. Herein, polyphenol-mediated ZIF-8 nanoparticles with hydroxyl-rich hollow structure were synthesized by tannic acid tailored regulation. PA-based membranes with fast penetration, high retention, and precise Cl<sup>−</sup>/SO<sub>4</sub><sup>2−</sup> selection were then synthesized through spatially and temporally controlling interfacial polymerization with modified ZIF-8 nanoparticles (tZIF-8) as aqueous phase additives or as interlayers. The effects of the embedding position of tZIF-8 on the structure, morphology, physicochemical properties, and performance of PA-based membranes were explored through a sequence of characterization techniques. The results revealed that the PA-based membrane with tZIF-8 embedded in the PA layer could achieve a high water permeance of 24.8 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> with a high retention of 99.4 % Na<sub>2</sub>SO<sub>4</sub> and a Cl<sup>−</sup>/SO<sub>4</sub><sup>2−</sup> selectivity of 141, which was superior to most state-of-the-art PA-based membranes. Comparatively, the Cl<sup>−</sup>/SO<sub>4</sub><sup>2−</sup> selection of the PA-based membrane with tZIF-8 embedded between the PA layer and the substrate was 136, while the water permeance was slightly enhanced to 28.2 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>. Excitingly, the resulting membranes all exhibit superior antifouling properties and stability. Our facile strategy for tuning membrane microstructures provides new ideals into the development of highly permeable and excellently selective PA-based membranes for precise ion sieving.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123435"},"PeriodicalIF":8.4,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142534722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ultrathin membranes comprising polymers of intrinsic microporosity oligomers for high-performance organic solvent nanofiltration 用于高性能有机溶剂纳滤器的由本征微孔低聚物聚合物组成的超薄膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-20 DOI: 10.1016/j.memsci.2024.123436

Yehao Jin , Aiwen Zhang , Guanying Dong , Jingwei Hou , Junyong Zhu , Yatao Zhang

Microporous organic polymers (MOPs) featuring chemically rigid backbones and permanent micropores are desirable for fabricating molecular selective membranes towards organics separation. However, coordinating facile film processing with high micropore persistence remains a challenge. In this paper, a low molecular weight polymers of intrinsic microporosity was rationally designed by precisely controlling the stoichiometric equilibrium of polymerization monomer. The polymers of intrinsic microporosity oligomers combine rigid and contorted structures with the aqueous solution processability, promoting the formation of 25-nm-thick polyaramide nanofilms with enhanced microporosity via support-free interfacial polymerization (SFIP). The resulting composite membranes have superior retention of small molecular solutes and high nonpolar and polar solvent permeances. Experiment and simulation results show that their excellent separation performance is due to substantially open and interconnected microporosity formed in the polymer networks based on rigid and contorted diamines as well as reduced film thickness. This study provides a new sight for using MOPs to construct high-microporosity membranes for precise and rapid molecular sieving.

具有化学刚性骨架和永久微孔的微孔有机聚合物（MOPs）是制造有机物分离分子选择膜的理想材料。然而，协调薄膜加工的简便性和高微孔持久性仍是一个挑战。本文通过精确控制聚合单体的化学平衡，合理设计了一种具有固有微孔的低分子量聚合物。本征微孔聚合物低聚物将刚性和扭曲结构与水溶液加工性结合起来，通过无支撑界面聚合（SFIP）促进形成 25 纳米厚的具有增强微孔的聚芳酰胺纳米膜。由此产生的复合膜具有出色的小分子溶质截留能力和较高的非极性和极性溶剂渗透率。实验和模拟结果表明，其优异的分离性能得益于基于刚性和变形二胺的聚合物网络中形成的大量开放和相互连接的微孔，以及膜厚度的降低。这项研究为利用 MOPs 构建高微孔膜以实现精确、快速的分子筛分提供了新的视角。

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引用次数: 0

Zwitterionic covalent organic framework membranes for efficient liquid molecular separations 用于高效液体分子分离的共价离子有机框架膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-19 DOI: 10.1016/j.memsci.2024.123433

Ye Zhang , Mengqing Liu , Yifan Wu , Jing Zhao , Guangfeng Liu , Shiyuan Zhou , Peng Wang , Peiyang Gu

Covalent organic frameworks (COFs) featuring uniform topological structure and devisable functionality have emerged as promising membrane materials. The design and precise manipulation of COF membranes with advanced spatial structure to achieve efficient liquid molecular separations are of great necessity. Herein, zwitterionic COF membranes have been in-situ fabricated on porous polymeric substrates using an interfacial polymerization modification strategy. The continuous defect-free COF membranes with two-dimensional in-plane dominant growth can be achieved by optimizing the fabrication parameters including reaction time, monomer concentration, and catalyst concentration. Subsequent zwitterionic modification thereon not only favors the formation of hydrophilic surface but also improves the sieving capability by sheltering effect. Attributed to the synergistic contribution, the optimized zwitterionic COF membrane possesses a superior separation factor of 2839 with the water content in the permeate up to 99.7 wt%, while maintaining a comparable permeation flux of 3309 g m⁻² h⁻¹ during the ethanol dehydration process, outperforming most of other representative membranes. Furthermore, the excellent durability of the zwitterionic COF membrane in the ethanol dehydration process and its efficient separation performance towards other alcohol dehydration systems demonstrate its potential practical applications. The easy scalability of the fabrication and regulation method offers crucial guidance for the engineering of advanced COF membranes in efficient liquid molecular separations.

具有均匀拓扑结构和可设计功能的共价有机框架（COFs）已成为前景广阔的膜材料。设计和精确操纵具有先进空间结构的 COF 膜以实现高效的液体分子分离是非常必要的。本文采用界面聚合改性策略，在多孔聚合物基底上原位制备了齐聚物 COF 膜。通过优化包括反应时间、单体浓度和催化剂浓度在内的制备参数，可以制备出具有二维面内优势生长的连续无缺陷 COF 膜。随后对其进行的齐聚物改性不仅有利于形成亲水性表面，还能通过遮蔽效应提高筛分能力。由于协同作用，优化后的 Zwitterionic COF 膜在乙醇脱水过程中，在渗透物含水量高达 99.7 wt% 的情况下，分离因子高达 2839，同时保持了 3309 g m-2 h-1 的可比渗透通量，优于大多数其他代表性膜。此外，两性离子 COF 膜在乙醇脱水过程中的出色耐久性及其对其他酒精脱水系统的高效分离性能也证明了其潜在的实际应用价值。制造和调节方法的易扩展性为先进 COF 膜在高效液体分子分离中的工程应用提供了重要指导。

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引用次数: 0

Enhancing separation performance of thin film nanocomposite membranes by self-etching of polydopamine-modified calcium carbonate during interfacial polymerization process 通过在界面聚合过程中自酸蚀聚多巴胺改性碳酸钙来提高薄膜纳米复合膜的分离性能

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-18 DOI: 10.1016/j.memsci.2024.123392

Xinxin Wei , Xuelin Wang , Kaiming Fan , Yanling Liu , Shengji Xia

The acid-accepting and gas-generating properties, along with the formation of extensive nanovoids, make CaCO₃ nanoparticles attractive as sacrificial nanofillers for fabricating thin-film composite (TFN) nanofiltration membranes. However, challenges such as severe agglomeration and limited acid etching efficiency of the nanoparticles hinder the pursuit of superior membrane performance. In this study, the dispersion and compatibility of CaCO₃ nanoparticles within the membrane matrix were improved by modifying them with a polydopamine (PDA) coating. The abundant phenolic hydroxyl groups of PDA enhanced the hydrophilicity and negative charges of membrane surface. Additionally, the PDA capsule increased the etching extent of the CaCO₃ nanoparticles by improving the nanoparticle dispersion and generating additional acid, which created sufficient water channels within the polyamide layer. It was demonstrated that incorporating 45 μg/cm² of PDA-modified CaCO₃ nanoparticles doubled the water permeance to 16.7 LMH/bar, while maintaining a low molecular weight cut-off of 249 Da and achieving rejections over 90 % for five types of per- and polyfluorinated substances. The PDA modification also overcame the membrane stability issue caused by the agglomerated CaCO₃ nanoparticles. This study provides a novel strategy for applying properly modified self-etching nanofillers in TFN membrane development, showing great potential for water treatment applications.

CaCO3 纳米粒子具有接受酸和产生气体的特性，并能形成大量纳米固体，因此可作为牺牲性纳米填料用于制造薄膜复合（TFN）纳滤膜。然而，纳米颗粒的严重团聚和有限的酸蚀刻效率等挑战阻碍了对卓越膜性能的追求。在本研究中，通过使用聚多巴胺（PDA）涂层对 CaCO3 纳米粒子进行改性，改善了它们在膜基质中的分散性和相容性。PDA 中丰富的酚羟基增强了膜表面的亲水性和负电荷。此外，PDA 胶囊通过改善纳米颗粒的分散性和产生额外的酸，在聚酰胺层内形成足够的水通道，从而提高了 CaCO3 纳米颗粒的蚀刻程度。实验证明，加入 45 μg/cm2 的 PDA 改性 CaCO3 纳米粒子后，透水性提高了一倍，达到 16.7 LMH/bar，同时保持了 249 Da 的低分子量截止值，对五种全氟和多氟物质的阻隔率超过 90%。PDA 改性还克服了 CaCO3 纳米颗粒团聚造成的膜稳定性问题。这项研究为在 TFN 膜开发中应用适当改性的自咬合纳米填料提供了一种新策略，在水处理应用中显示出巨大的潜力。

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引用次数: 0

Multi-channeled halloysite nanotube-blended polybenzimidazole separators for enhancing lithium-ion battery performance 用于提高锂离子电池性能的多通道霍洛石纳米管混合聚苯并咪唑隔膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-18 DOI: 10.1016/j.memsci.2024.123417

Qian Zhou , Shabab Hussain , Jinwu Peng , Bin Zhang , Lei Wang

The microscopic transport mode of lithium ions in the separator is crucial for solving the problem of irregular lithium dendrite growth, thereby enhancing the safety of battery operation, and it also has a positive impact on the electrochemical performance of the battery. Furthermore, the heat resistance of the separator is an important indicator for measuring the performance of the separator and the safety of battery usage. In this work, we have introduced sulfonated and lithiated halloysite nanotubes into a high-temperature-resistant OPBI matrix through an easily implementable NIPS, resulting in a high-temperature-resistant separator with multiple lithium-ion micro-transport morphologies. Lithium ions can shuttle through the halloysite nanotube pores, negatively charged sulfonate groups on the surface, and larger finger-like pores formed by NIPS within the separator, creating a high and uniform lithium-ion flux that prevents excessive localized ion flow leading to the aggressive growth of lithium dendrites. According to the characterization data, this separator exhibits relatively satisfactory performance, such as an ionic conductivity of 1.82 mS cm⁻¹, a porosity of 82 %, an electrolyte uptake of 397 %, and no significant physical shrinkage at 200 °C. Additionally, the cells assembled using the OPBI@sHNT-Li20 separator delivers higher discharge capacity (164.92 mAh·g⁻¹), more stable cycle, superior rate performance. So the OPBI@sHNT-Li separator is expected to play an active role in improving the safety and electrochemical performance of lithium-ion batteries.

锂离子在隔膜中的微观传输模式对于解决锂枝晶的不规则生长问题至关重要，从而提高电池运行的安全性，同时也对电池的电化学性能产生积极影响。此外，隔膜的耐热性也是衡量隔膜性能和电池使用安全性的重要指标。在这项工作中，我们通过一种易于实现的 NIPS，将磺化和锂化的哈洛来石纳米管引入耐高温的 OPBI 基体中，从而得到了一种具有多种锂离子微传输形态的耐高温隔膜。锂离子可以穿梭于埃洛石纳米管孔隙、表面带负电荷的磺酸盐基团以及由 NIPS 在分离器内形成的较大的指状孔隙中，从而产生高且均匀的锂离子通量，防止过度的局部离子流导致锂枝晶的侵蚀生长。根据表征数据，这种隔膜的性能比较令人满意，例如离子电导率为 1.82 mS cm-1，孔隙率为 82%，电解质吸收率为 397%，在 200 °C 时没有明显的物理收缩。此外，使用 OPBI@sHNT-Li20 隔离层组装的电池具有更高的放电容量（164.92 mAh-g-1）、更稳定的循环和更优越的速率性能。因此，OPBI@sHNT-Li 隔膜有望在提高锂离子电池的安全性和电化学性能方面发挥积极作用。

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引用次数: 0

In-situ growth of three-dimensional copper-based catalyst in 4A zeolite/PES mixed matrix membrane for Fenton-like degradation of phenol 在 4A 沸石/聚醚砜混合基质膜中原位生长三维铜基催化剂，用于苯酚的芬顿降解

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-18 DOI: 10.1016/j.memsci.2024.123407

Jing Lv , Han Zhang , Hui Ye, Xiaojian Fu, Shurui Han, Guodong Yang, Jinli Zhao, Lizhi Zhao, Qingping Xin, Ligang Lin, Xiaoli Ding, Hong Li, Yuzhong Zhang

Fenton-like membrane reactors applied to water purification provide a broad solution to address the challenges of catalyst recovery, low reaction efficiency, and high mass transfer resistance in heterogeneous batch reactions. Zeolites as nanocatalyst carriers are promising candidates for advanced purification membranes. Herein, we report a composite catalytic membrane (4A-Cu/PES) for Fenton-like degradation of phenol wastewater, fabricated by in-situ growth of copper nanoflowers on a 4A zeolite/polyethersulfone (PES) mixed matrix membrane, forming a three-dimensional core-shell nanostructured catalyst. Compared with the conventional method, the in-situ growth prevents the copper catalyst from being covered by the polymer and significantly increases the copper loading (3.97 %), thus ensuring efficient catalytic reactions within the membrane pores. Meanwhile, the porous structure of zeolite provides a large specific surface area, facilitating uniform dispersion of copper ions during in situ growth of the catalyst and providing abundant active sites. The membrane exhibited a phenol degradation rate of 93.9 % at pH 6, significantly broadening the pH applicability of the Fenton reaction. Hydroxyl radicals (·OH) were identified as the primary active species in the 4A-Cu/PES-H₂O₂ system. Moreover, the membrane retained high catalytic activity after five cycles, demonstrating excellent stability. This work provides important insights for designing efficient and stable Fenton-like zeolite catalytic membranes.

应用于水净化的类芬顿膜反应器为解决异相批量反应中的催化剂回收、低反应效率和高传质阻力等难题提供了广泛的解决方案。作为纳米催化剂载体的沸石是先进净化膜的理想候选材料。在此，我们报告了一种用于苯酚废水 Fenton 类降解的复合催化膜（4A-Cu/PES），它是通过在 4A 沸石/聚醚砜（PES）混合基质膜上原位生长铜纳米流，形成三维核壳纳米结构催化剂而制成的。与传统方法相比，原位生长可防止铜催化剂被聚合物覆盖，并显著提高铜负载量（3.97%），从而确保膜孔内的高效催化反应。同时，沸石的多孔结构提供了较大的比表面积，有利于铜离子在催化剂原位生长过程中均匀分散，并提供了丰富的活性位点。该膜在 pH 值为 6 时的苯酚降解率为 93.9%，大大拓宽了芬顿反应的适用 pH 值。羟基自由基（-OH）被确定为 4A-Cu/PES-H2O2 系统中的主要活性物种。此外，该膜在五个循环后仍能保持较高的催化活性，显示出卓越的稳定性。这项研究为设计高效稳定的类芬顿沸石催化膜提供了重要启示。

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