Journal of Membrane Science最新文献_第9页

Crown ether-functionalized nanofiltration membranes with high ions selectivity for Li+/Mg2+ separation 用于分离 Li+/Mg2+ 的高离子选择性冠醚功能化纳滤膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-05 DOI: 10.1016/j.memsci.2024.123372

Chi Jiang , Shibo Bai , Jiawang Li , Ming Wang , Yan Zhou , Yingfei Hou

Extraction of lithium resources from salt lake brines is an effective method to solve the shortage of lithium resources nowadays. However, magnesium-lithium separation has become a critical issue for lithium extraction from salt lakes with high Mg²⁺/Li⁺ ratio, due to the similar ionic characteristics of Li⁺ (0.38 nm), and Mg²⁺ (0.43 nm). Herein, an amine monomer containing crown ether group (4′-aminobenzo-15-crown-5-ether (NH₂–B15C5)) was introduced into the interfacial polymerization (IP) process of piperazine (PIP) and homotrimethylene tricarbonyl chloride (TMC) to prepare polyamide (PA) nanofiltration (NF) membranes with Li⁺ selective transport channels. NH₂–B15C5 shows good compatibility and selective complexation to Li⁺, which acts as Li⁺ selective transport channels effectively retaining Mg²⁺ and allowing Li⁺ to cross the membrane smoothly, therefore solving the problem of poor lithium-magnesium separation performance of most of the NF membranes currently. Molecular dynamics simulations (MD) also confirmed that NH₂–B15C5 has a stronger affinity for Li⁺ than for Mg²⁺. The NH₂–B15C5/PIP-TMC membrane exhibited excellent separation performance and water permeance in simulated salt lake brine (2000 ppm, W_Mg/Li = 100), where the S_{Li, Mg} and water permeance were 32.2 and 8.22 L·m⁻²·h⁻¹·bar⁻¹. Importantly, the crown ether is introduced into the PA separator layer in the form of covalent bonds, hence showing excellent stability. Overall, an NF membrane with high lithium-magnesium separation performance was designed for the extraction of lithium resources from high Mg²⁺/Li⁺ ratio salt lake brine.

从盐湖卤水中提取锂资源是解决当今锂资源短缺的有效方法。然而，由于 Li+（0.38 nm）和 Mg2+（0.43 nm）具有相似的离子特性，镁锂分离已成为从 Mg2+/Li+ 比率较高的盐湖中提取锂的关键问题。本文在哌嗪（PIP）和均三亚甲基三羰酰氯（TMC）的界面聚合（IP）过程中引入了一种含冠醚基团的胺单体（4′-氨基苯并-15-冠-5-醚（NH2-B15C5）），以制备具有 Li+ 选择性传输通道的聚酰胺（PA）纳滤膜（NF）。NH2-B15C5 与 Li+ 具有良好的相容性和选择性络合，可作为 Li+ 的选择性传输通道，有效截留 Mg2+，使 Li+ 顺利穿过膜，从而解决了目前大多数纳滤膜锂镁分离性能差的问题。分子动力学模拟（MD）也证实了 NH2-B15C5 对 Li+ 的亲和力强于对 Mg2+的亲和力。NH2-B15C5/PIP-TMC 膜在模拟盐湖盐水（2000 ppm，WMg/Li = 100）中表现出优异的分离性能和透水性，其中 SLi、Mg 和水的渗透率分别为 32.2 和 8.22 L-m-2-h-1-bar-1。重要的是，冠醚是以共价键的形式进入 PA 分离层的，因此表现出卓越的稳定性。总之，针对从高 Mg2+/Li+ 比率盐湖卤水中提取锂资源，设计出了一种具有高锂镁分离性能的 NF 膜。

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引用次数: 0

Impact of side chain length on the properties and alkaline fuel cell performance of OEG-grafted poly(terphenyl piperidinium) anion exchange membranes 侧链长度对 OEG 接枝聚（三联苯哌啶）阴离子交换膜的特性和碱性燃料电池性能的影响

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-28 DOI: 10.1016/j.memsci.2024.123375

Jingjing Zhang , Runan Shao , Tongxin Yin , Dongrui Chu , Xiaojuan Zhang , Nanwen Li , Lei Liu

In designing comb-shaped anion exchange membranes (AEMs), replacing alkyl side chains with ethylene glycol (EG)-based ones significantly enhances membrane properties and boosts AEM fuel cell performance. Although much research has focused on optimizing the placement of EG segments within the polymer matrix, the effect of EG chain length remains less explored. In this work, a series of poly(terphenyl piperidinium) AEMs with N-oligo(ethylene glycol) (OEG) terminal pendants having two to five EG repeating units were prepared by simple post-polymerization quaternization. The membrane properties showed a strong correlation with the length of the OEG side chains, influenced by both chemical composition and phase behavior. Among the OEG-grafted AEMs, PTP-OEG3 with moderate three EG repeating units, exhibited the best properties due to a careful balance between EG and cationic groups, leading to a favorable microphased separation. It achieved high hydroxide conductivity (114 mS cm⁻¹ at 80 °C in water), robust mechanical strength (tensile strength >52 MPa), and good ex situ alkaline stability. As a result, the AEM fuel cells with the property-balanced PTP-OEG3 membrane achieved the highest peak power density of 976 mW cm⁻². The in situ stability of these AEMs was also investigated. Evidently, understanding the optimal EG side chain length is an important criterion for designing AEM materials for alkaline fuel cells.

在设计梳状阴离子交换膜（AEM）时，用乙二醇（EG）侧链取代烷基侧链可显著增强膜的性能并提高 AEM 燃料电池的性能。虽然许多研究都集中在优化 EG 段在聚合物基质中的位置，但对 EG 链长的影响的探索仍然较少。在这项工作中，通过简单的聚合后季铵化法制备了一系列具有 N-榄香烯（乙二醇）（OEG）末端垂体的聚三联苯哌啶 AEM，这些末端垂体具有 2 到 5 个 EG 重复单元。膜的特性与 OEG 侧链的长度密切相关，同时受到化学成分和相行为的影响。在 OEG 接枝的 AEM 中，PTP-OEG3 具有适度的三个 EG 重复单元，由于 EG 和阳离子基团之间的良好平衡而表现出最佳性能，从而实现了有利的微相分离。它具有较高的氢氧化物传导性（在 80 °C 水中为 114 mS cm-1）、较强的机械强度（拉伸强度为 52 兆帕）和良好的原位碱性稳定性。因此，采用性能平衡 PTP-OEG3 膜的 AEM 燃料电池达到了 976 mW cm-2 的最高峰值功率密度。此外，还对这些 AEM 的原位稳定性进行了研究。由此可见，了解最佳的 EG 侧链长度是设计碱性燃料电池 AEM 材料的一个重要标准。

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引用次数: 0

Flux and fouling behavior during constant pressure sterile filtration of nanoemulsions 纳米乳液恒压无菌过滤过程中的流量和堵塞行为

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-27 DOI: 10.1016/j.memsci.2024.123370

Shreya Kapila , Randal J. Soukup , Marissa E. Bradley , Andrew L. Zydney

Nanoemulsions with droplet diameters from 20 to 200 nm have emerged as attractive adjuvants in the development of novel vaccines and as an advanced method of drug delivery for hydrophobic drugs. However, the large size of the nanoemulsion droplets leads to very low capacities during the final sterile filtration step used to ensure sterility of parenteral drug products. The objective of this study was to examine the sterile filtration of a model nanoemulsion made using squalene as the oil and Tween 20 and Span 85 as stabilizing surfactants. Data were obtained with different commercial sterile filters with different morphology and chemistry during constant pressure filtration. In each case, there was essentially no filtration until the transmembrane pressure exceeded a critical value related to the force required to push the deformable nanoemulsion droplets through the membrane pores. The filter capacity increased with increasing pressure, going from 700 g/m² at 140 kPa to 1300 g/m² at 280 kPa for a dual layer polyethersulfone sterile filter, with the flux decline well described by the complete pore blockage model. The dual layer asymmetric membranes showed much higher capacities than corresponding single layer filters due to the effectiveness of the upper layer in removing larger nanoemulsion droplets that would otherwise block the pores of the sterile filter. The capacity of the different sterile filters was also well-correlated with the initial filtrate flux, with both of these parameters governed by the pore size distribution and surface chemistry of the filters. These results provide important insights into factors controlling the sterile filtration of highly concentrated nanoemulsions used in the formulation of vaccines and drug products.

液滴直径在 20 纳米到 200 纳米之间的纳米乳液已成为新型疫苗开发过程中极具吸引力的佐剂，也是疏水性药物的一种先进给药方法。然而，由于纳米乳液液滴的尺寸较大，因此在用于确保肠外药物产品无菌性的最后无菌过滤步骤中，纳米乳液的容量非常低。本研究的目的是检测以角鲨烯为油、吐温 20 和司潘 85 为稳定表面活性剂制成的纳米乳液模型的无菌过滤情况。在恒压过滤过程中，使用不同形态和化学性质的商用无菌过滤器获得了数据。在每种情况下，在跨膜压力超过与推动可变形的纳米乳液液滴通过膜孔所需的力有关的临界值之前，基本上没有过滤。过滤能力随着压力的增加而增加，双层聚醚砜无菌过滤器的过滤能力从 140 kPa 时的 700 g/m2 增加到 280 kPa 时的 1300 g/m2，完全孔隙堵塞模型很好地描述了通量的下降。双层不对称膜的过滤能力远远高于相应的单层过滤器，这是因为上层能有效去除较大的纳米乳液液滴，否则这些液滴会堵塞无菌过滤器的孔隙。不同无菌过滤器的容量也与初始滤液通量密切相关，这两个参数都受过滤器孔径分布和表面化学性质的影响。这些结果为了解疫苗和药物产品配方中使用的高浓度纳米乳剂的无菌过滤控制因素提供了重要的启示。

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引用次数: 0

Robust branched Poly(p-terphenyl isatin) anion exchange membranes with enhanced microphase separation structure for fuel cells 用于燃料电池的具有增强微相分离结构的稳健支化聚（对三联苯靛蓝）阴离子交换膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-26 DOI: 10.1016/j.memsci.2024.123368

Yijia Lei , Jialin Zhao , Jian Gao , Jingyi Wu , Na Li , Xiaoyu Chi , Yan Wang , Yiman Gu , Zhe Wang

Anion exchange membrane fuel cells (AEMFCs) are gradually becoming the focus of sustainable hydrogen energy research due to the advantages of clean by-products, faster oxidation-reduction dynamics and allowing cheap platinum-free base materials. As the key components of AEMFCs, anion exchange membranes (AEMs) are required to have high ionic conductivity and dimensional stability. This study focused on the design and preparation of branched AEMs for AEMFCs. The b-PTIN-x membranes were generated by incorporating 1,3,5-triphenylbenzene (TPB) units into rigid poly(p-terphenyl isatin) (PTI) polymer backbones. This innovative approach aimed to induce microphase separation structures by exploiting TPB with high FFV, as well as to enhance the tensile strength of AEMs with the help of branched structures. SAXS and AFM images revealed that the AEMs achieved enhanced microphase separation structures, resulting in the formation of ion transport channels with dimensions in the range of a few nanometers (3.36–3.70 nm). The branched b-PTIN-11 membranes displayed significant OH⁻ conductivity (153.9 mS cm⁻¹ at 80 °C) while having a low ion exchange capacity (IEC) (1.73 mmol g⁻¹). The b-PTIN-11 membranes displayed improved tensile strength (56.69 MPa) and exceptional dimensional stability, with swelling ratio (SR) of 18.5 % at 80 °C. They also showed great chemical stability with 89.64 % conductivity remaining, lasting for more than 1200 h in 3 M NaOH solution at 80 °C. Ultimately, the b-PTIN-11 membrane underwent testing to evaluate its performance in a fuel cell using H₂–O₂. It demonstrated a peak power density (PPD) of 566 mW cm⁻² when subjected to a current density of 1339 mA cm⁻².

阴离子交换膜燃料电池（AEMFCs）具有副产品清洁、氧化还原动力学速度快、无铂基础材料便宜等优点，正逐渐成为可持续氢能研究的重点。作为 AEMFC 的关键部件，阴离子交换膜（AEM）需要具有高离子传导性和尺寸稳定性。本研究的重点是设计和制备用于 AEMFC 的支化 AEM。b-PTIN-x 膜是通过将 1,3,5-三苯基苯（TPB）单元加入刚性聚（对三联苯异铂）（PTI）聚合物骨架而产生的。这种创新方法的目的是利用 TPB 的高 FFV 诱导微相分离结构，并借助支化结构增强 AEM 的拉伸强度。SAXS 和原子力显微镜图像显示，AEMs 实现了增强的微相分离结构，形成了尺寸在几纳米（3.36-3.70 nm）范围内的离子传输通道。支化 b-PTIN-11 膜具有显著的 OH- 导电性（80 °C 时为 153.9 mS cm-1），而离子交换容量（IEC）较低（1.73 mmol g-1）。b-PTIN-11 膜显示出更高的抗拉强度（56.69 兆帕）和优异的尺寸稳定性，80 °C 时的膨胀率（SR）为 18.5%。它们还表现出极高的化学稳定性，在 80 °C 的 3 M NaOH 溶液中可保持 89.64% 的电导率，持续时间超过 1200 小时。最后，对 b-PTIN-11 膜进行了测试，以评估其在使用 H2-O2 的燃料电池中的性能。当电流密度为 1339 mA cm-2 时，其峰值功率密度 (PPD) 为 566 mW cm-2。

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引用次数: 0

Hydrothermally rearranged cellulose membranes for controlled size sieving 用于控制筛分尺寸的水热重排纤维素膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-25 DOI: 10.1016/j.memsci.2024.123367

Inho Park , Jun Hyeok Kang , Yelim Ha, Junhyeong Lee, Ho Bum Park

Biodegradable polymers are important for reducing pollution and promoting sustainability as they break down more easily than traditional petroleum-based polymers. One such polymer is regenerated cellulose (RC), which is widely used in water purification and pharmaceuticals due to its chemical resistance and hydrophilicity. Since its direct use of cellulose is limited by its insolubility, derivatives like cellulose acetate (CA) are first converted through a regeneration process back into RC to make use of its functional properties. During this process, however, the membrane structure may be compromised, impairing its separation performance. Here we show that simply soaking CA membranes in hot water before regeneration significantly improves the structural integrity of RC membranes, retaining the sieving properties. The pretreatment causes planar shrinkage without disrupting the general characteristics of cellulose, allowing for sole adjustment of pore size. This straightforward approach enables precise tuning of membrane pore properties to suit specific application, such as adjusting pore size for efficient sieving of materials with particular molecular masses, all while maintaining high water permeance. Our findings suggest that hydrothermal processing has the potential to enhance the filtration performance of RC membranes and broaden their range of applications.

可生物降解聚合物比传统的石油基聚合物更容易分解，因此对减少污染和促进可持续发展非常重要。再生纤维素（RC）就是这样一种聚合物，因其耐化学腐蚀性和亲水性，被广泛应用于水净化和制药领域。由于纤维素的不溶性限制了它的直接使用，醋酸纤维素（CA）等衍生物首先要通过再生过程转化回 RC，以利用其功能特性。但在这一过程中，膜结构可能会受到破坏，从而影响其分离性能。在这里，我们展示了在再生之前只需将 CA 膜浸泡在热水中，就能显著改善 RC 膜的结构完整性，并保持其筛分性能。预处理会导致平面收缩，但不会破坏纤维素的一般特性，从而可以单独调整孔径大小。这种直接的方法可以精确调整膜的孔隙特性，以适应特定的应用，例如调整孔隙大小以有效筛分具有特定分子质量的材料，同时保持高透水性。我们的研究结果表明，水热处理有可能提高 RC 膜的过滤性能，并扩大其应用范围。

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引用次数: 0

Interfacial oligomer splicing toward 3D silicon-centered polyimine nanofilm for rapid molecule/ion differentiation 面向三维硅中心聚酰亚胺纳米薄膜的界面低聚物拼接，实现分子/离子快速分化

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-25 DOI: 10.1016/j.memsci.2024.123354

Lei Ge , Tiantian Chen , Zongkai Liu , Yizhuo Li , Honghao Su , Junyong Zhu , Yatao Zhang , Bart Van der Bruggen

3D porous organic polymers —renowned for rich interpenetrated, hierarchical pores and exceptional structural durability— showcase the potential for precise membrane-based separations. However, the challenge lies in processing these chemically stable polymers into a selective thin film under mild conditions. Herein, an interfacial oligomer splicing (IOS) approach via Schiff-base reactions is presented to create 3D silicon-centered porous polyimine (PPIn) nanofilms. The pre-synthesized oligomers from 4,4′,4″,4‴-silanetetrayltetrabenzaldehyde (TFS) and m-phenylenediamine (MPD) with high steric hindrance and hydrophobic character are precisely confined at the oil boundary, initiating IOS to yield an amorphous nanofilm on a Kevlar hydrogel surface. These silicon-centered 3D nanofilms exhibited an exceptional thermal and mechanical stability, while offering abundant low-resistance transport nanochannels. The nanofilm backbone, composed of rigid nonplanar aromatic skeleton and robust imine linkage, contributed to open and interpenetrated selective nanochannels, corroborated by both experimental and simulation and results. It was shown that 83-nm-thick PPIn nanofilms grown on the hydrogel achieved high-efficient molecule/ion differentiation, evident in excellent dye retention (>99.0 %), high NaCl permeation (92.8 %), and remarkable water permeability (74.3 L m⁻² h⁻¹ bar⁻¹). This study establishes an innovative IOS approach for fabricating silicon-centered 3D-POP membranes and underscores their potential for efficient molecule/ion differentiation.

三维多孔有机聚合物因其丰富的互穿、分层孔隙和优异的结构耐久性而闻名于世，展示了基于膜的精确分离的潜力。然而，将这些化学性质稳定的聚合物在温和的条件下加工成选择性薄膜是一项挑战。本文介绍了一种通过席夫碱反应的界面低聚物拼接（IOS）方法，用于制造三维硅中心多孔聚酰亚胺（PPIn）纳米薄膜。预先合成的 4,4′,4″,4‴-硅四乙基四苯甲醛（TFS）和间苯二胺（MPD）低聚物具有高立体阻碍和疏水特性，它们被精确地限制在油边界上，启动 IOS 在 Kevlar 水凝胶表面生成无定形纳米薄膜。这些以硅为中心的三维纳米薄膜具有优异的热稳定性和机械稳定性，同时提供了丰富的低阻力传输纳米通道。纳米薄膜骨架由刚性非平面芳香族骨架和坚固的亚胺连接组成，有助于形成开放和相互渗透的选择性纳米通道，实验和模拟结果均证实了这一点。实验和模拟结果表明，在水凝胶上生长的 83 纳米厚的 PPIn 纳米薄膜实现了高效的分子/离子分化，表现为出色的染料保留率（99.0%）、高氯化钠渗透率（92.8%）和显著的透水性（74.3 L m-2 h-1 bar-1）。这项研究确立了一种创新的 IOS 方法，用于制造以硅为中心的 3D-POP 膜，并强调了它们在高效分子/离子分化方面的潜力。

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引用次数: 0

Study on the effect mechanism of functional graphene oxide on the performance of polymer electrolyte membrane for fuel cells 功能性氧化石墨烯对燃料电池聚合物电解质膜性能的影响机理研究

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-24 DOI: 10.1016/j.memsci.2024.123359

Kuirong Feng , Pengyun Zhao , Na Li , Fenglong Chen , Jiayin Wang , Lingxin Meng , Wei Fan , Jingmei Xu

In this paper, amino-phosphate bifunctionalized graphene oxide (PA-GO) was successfully synthesized by amination reaction of graphene oxide followed by acid modification with hypophosphorous acid. A series of composite proton exchange membranes were successfully prepared by adding modified GO to sulfonated poly (aryl ether ketone sulfone) matrices containing carboxyl groups (C-SPAEKS). The prepared composite membranes were performed by a series of tests. The C-SPAEKS@1%PA-GO had the best performance, which was able to achieve the tensile strength of 42 MPa while possessing the high proton conductivity of 128.23 mS cm⁻¹ at 80 °C. In addition, the peak power density of C-SPAEKS@1%PA-GO reached 677.67 mW cm⁻² at a current density of 2082.8 mA cm⁻², which was almost four times that of the pure membrane (166 mW cm⁻²). And after 44 h at a constant current density of 0.1 A cm⁻², the C-SPAEKS@1%PA-GO membrane could still maintain 54.1 % of the original voltage. It can be seen that our work has achieved certain results, and the functionalized modification of graphene oxide could greatly improve the comprehensive performance of proton exchange membranes (PEMs).

本文通过对氧化石墨烯进行胺化反应，然后用次磷酸进行酸性改性，成功合成了氨基-磷酸双官能化氧化石墨烯（PA-GO）。在含有羧基的磺化聚（芳基醚酮砜）基质（C-SPAEKS）中加入改性的 GO，成功制备了一系列复合质子交换膜。对制备的复合膜进行了一系列测试。C-SPAEKS@1%PA-GO的性能最佳，在80 °C时能够达到42兆帕的拉伸强度，同时具有128.23毫秒/厘米-1的高质子传导率。此外，在电流密度为 2082.8 mA cm-2 时，C-SPAEKS@1%PA-GO 的峰值功率密度达到 677.67 mW cm-2，几乎是纯膜（166 mW cm-2）的四倍。而在 0.1 A cm-2 的恒定电流密度下 44 小时后，C-SPAEKS@1%PA-GO 膜仍能保持原始电压的 54.1%。由此可见，我们的工作取得了一定的成果，氧化石墨烯的功能化改性可以大大提高质子交换膜（PEM）的综合性能。

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引用次数: 0

Polyelectrolyte-modified covalent organic framework membranes for multivalent cation removal 用于去除多价阳离子的聚电解质改性共价有机框架膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-24 DOI: 10.1016/j.memsci.2024.123363

Yu Zheng , Zixu Yang , Zhichao Li , Wangluo Liu , Chao Yang , Jianliang Shen , Hui Wang , Kai Xu , Lijuan Cheng , Runnan Zhang , Zhongyi Jiang

Covalent organic framework (COF) has become a promising membrane material in chemical separations. However, the application of COF membranes for ion separation is still challenging, due to the mismatch between the pore size of COFs (1–5 nm) with the diameter of hydrated ions (<1 nm). Herein, a cationic polyelectrolyte surface modification strategy of COF membranes was proposed, by assembling a cationic polyelectrolyte (PEI, PDDA, PAH) layer on the surface of an anionic COF (TpPa-SO₃H) membrane via dip coating. The cationic polyelectrolytes on the membrane surface offered abundant positive charges and reduced the surface pore size, leading to the synergistic enhancement of the size sieving and the electrostatic repulsion. Accordingly, effective rejection of multivalent cations was realized with a significantly increased rejection rate of 97.1 % for MgCl₂, compared to that of TpPa-SO₃H membrane (10.3 %). Furthermore, the polyelectrolyte-modified COF membrane exhibited desirable separation performance for heavy metal ions in water. The rejection rates for heavy metal salts, including CrCl₃, CdCl_2, CuCl₂, PbCl₂ and NiCl₂, reached 98.5 %, 97.3 %, 97.0 %, 96.2 %, and 96.0 %, respectively, and remained above 95 % during the 7-day long-term operation test.

共价有机框架（COF）已成为化学分离领域一种前景广阔的膜材料。然而，由于 COF 的孔径（1-5 nm）与水合离子的直径（1 nm）不匹配，将 COF 膜用于离子分离仍具有挑战性。本文提出了一种阳离子聚电解质表面改性 COF 膜的策略，即通过浸涂法在阴离子 COF（TpPa-SO3H）膜表面组装阳离子聚电解质（PEI、PDDA、PAH）层。膜表面的阳离子聚电解质提供了丰富的正电荷并减小了表面孔径，从而协同增强了尺寸筛分和静电斥力。因此，与 TpPa-SO3H 膜（10.3%）相比，MgCl2 的阻隔率显著提高，达到 97.1%，实现了对多价阳离子的有效阻隔。此外，聚电解质改性 COF 膜对水中重金属离子也表现出理想的分离性能。重金属盐类（包括氯化铬、氯化镉、氯化铜、氯化铅和氯化镍）的去除率分别达到 98.5%、97.3%、97.0%、96.2% 和 96.0%，并且在 7 天的长期运行测试中保持在 95% 以上。

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引用次数: 0

Advanced lithium extraction nanofiltration membrane with fast transport channels via competitive diffusion and reaction of rigid electropositive phenylbiguanide molecules 通过刚性正电分子的竞争性扩散和反应实现具有快速传输通道的先进锂萃取纳滤膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-23 DOI: 10.1016/j.memsci.2024.123362

Yunhao Li , Haijun Yu , Lixin Li , Yanfang Liu , Guodong Kang , Xinmiao Liang , Yiming Cao

The utilization of nanofiltration membranes for lithium extraction from Salt-Lake holds the potential to address lithium resource scarcity and drive energy transformation. Nevertheless, the trade-off effect between water permeability and Mg²⁺/Li⁺ separation selectivity poses a challenge in the application of these membranes. In this work, rigid-flexible interpenetration and competitive diffusion reaction strategies were proposed to regulate the pore structure and charge density of the functional layer, thus enhancing the overall separation performance of nanofiltration membrane. Phenylbiguanide (PBG) possessing rigid structure, high positive charge density, and low energy transfer barrier was embedded into flexible polyethyleneimine-based polyamide network. This integration facilitated the formation of continuous and semi-permanent microcavities with rigid-flexible coupled structure, and meanwhile, elevated the density of positive charges. Consequently, the modification extended the water molecular transport channels within the functional layer, leading to a notable enhancement in pure water flux, from 7.40 to 26.43 L m⁻²h⁻¹. In addition, due to the faster diffusion of PBG than polyethyleneimine with high molecular weight (70000 Da, as aqueous monomer in this work), it could react with excess 1,3,5-trimesoyl chloride (TMC) on the surface of initial membrane to form a new polyamide layer, which repaired the defects in the functional layer and also enhanced the charge density inside pore channels. Therefore, Mg²⁺/Li⁺ separation selectivity factor increased from 3.79 of TFC membrane to 22.98 of PBG membrane, i.e., by about 6 times. This study provided an effective strategy to develop nanofiltration membranes with both good water permeability and Mg²⁺/Li⁺ selectivity.

利用纳滤膜从盐湖中提取锂有望解决锂资源稀缺的问题，并推动能源转型。然而，透水性和 Mg2+/Li+ 分离选择性之间的权衡效应给这些膜的应用带来了挑战。本研究提出了刚柔互穿和竞争扩散反应策略来调节功能层的孔隙结构和电荷密度，从而提高纳滤膜的整体分离性能。苯基双胍（PBG）具有刚性结构、高正电荷密度和低能量传递障碍，被嵌入到柔性聚乙烯亚胺基聚酰胺网络中。这种整合促进了具有刚柔耦合结构的连续半永久性微腔的形成，同时提高了正电荷密度。因此，这种改性扩展了功能层内的水分子传输通道，从而显著提高了纯水通量，从 7.40 升 m-2h-1 提高到 26.43 升 m-2h-1。此外，由于 PBG 的扩散速度快于高分子量的聚乙烯亚胺（7 万 Da，在本研究中为水单体），它可以与初始膜表面过量的 1,3,5-三甲基甲酰氯（TMC）反应，形成新的聚酰胺层，从而修复了功能层的缺陷，并提高了孔道内的电荷密度。因此，Mg2+/Li+ 分离选择因子从 TFC 膜的 3.79 提高到 PBG 膜的 22.98，即提高了约 6 倍。这项研究为开发具有良好透水性和 Mg2+/Li+ 选择性的纳滤膜提供了一种有效的策略。

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引用次数: 0

A novel dual-function antiscalant carboxymethyl cellulose-graft-protocatechuic acid for efficient scaling and biofouling prevention 一种新型的羧甲基纤维素-接枝原儿茶酸双重功能防垢剂，可有效防止结垢和生物污垢的产生

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-09-23 DOI: 10.1016/j.memsci.2024.123357

Liping Xiong , Wei Yu , Xinyi Lu , Jiaheng Teng , Cheng Chen , Bisheng Li , Liguo Shen , Hongjun Lin

Despite antiscalants playing a critical role in desalination and cooling water systems, their potential to support microbial growth pose a significant threat to water treatment processes by promoting biofouling. In this work, a novel dual-function antiscalant carboxymethyl cellulose-graft-protocatechuic acid (CMC-g-PA) was prepared using plant-derived antibacterial protocatechuic acid (PA) and natural polysaccharide cellulose, and its scale inhibition effect on CaSO₄ scale and antibacterial performance on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were evaluated. Results indicated that the inhibition efficiency against CaSO₄ scale and the induction time of CaSO₄ crystallization process in the presence of CMC-g-PA were remarkably enhanced compared to unmodified CMC. Microscope and XRD characterizations demonstrated significant alterations in the crystal morphology and size of the formed scale using CMC-g-PA as antiscalant. Molecular dynamics (MD) analysis also showed that CMC-g-PA could intensively interact with the crystal plane of CaSO₄ with the binding energy reaching 746.73 kcal/mol, thereby affecting crystal growth and causing crystal distortion. Additionally, an obvious inhibitory effect of CMC-g-PA on the growth of E. coli and S. aureus was observed, attributed primarily to the antibacterial activity of the introduced phenolic hydroxyl groups. In short, bio-derived CMC-g-PA, characterized in its environmental-friendliness, antiscaling efficiency and antibacterial activity, holds immense potential for mitigating scaling and biofouling in desalination/cooling water systems.

尽管防垢剂在海水淡化和冷却水系统中发挥着至关重要的作用，但其支持微生物生长的潜力会促进生物污垢的产生，从而对水处理工艺构成重大威胁。本研究利用植物源抗菌原儿茶酸（PA）和天然多糖纤维素制备了新型双功能防垢剂羧甲基纤维素-接枝原儿茶酸（CMC-g-PA），并评估了其对 CaSO4 的阻垢效果以及对大肠杆菌和金黄色葡萄球菌的抗菌性能。结果表明，与未改性的 CMC 相比，CMC-g-PA 对 CaSO4 结晶过程的抑制效率和诱导时间都显著提高。显微镜和 XRD 表征表明，使用 CMC-g-PA 作为抗垢剂后，晶体形态和形成的垢的大小发生了显著变化。分子动力学（MD）分析也表明，CMC-g-PA 与 CaSO4 的晶面有强烈的相互作用，结合能达到 746.73 kcal/mol，从而影响晶体生长并导致晶体变形。此外，还观察到 CMC-g-PA 对大肠杆菌和金黄色葡萄球菌的生长有明显的抑制作用，这主要归因于引入的酚羟基的抗菌活性。总之，生物衍生的 CMC-g-PA 具有环境友好性、防结垢效率和抗菌活性等特点，在减轻海水淡化/冷却水系统的结垢和生物污垢方面具有巨大潜力。

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引用次数: 0