Journal of Membrane Science最新文献_第3页

Self-assembled ILs-PVA micelle nanostructure impart the pervaporation membrane with high ethanol dehydration performance 自组装的 ILs-PVA 胶束纳米结构赋予渗透蒸发膜极高的乙醇脱水性能

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-05 DOI: 10.1016/j.memsci.2024.123481

Zakawat Ali , Xiaochun Zhang , Palwasha Khan , Jie Li , Nai Zhang , Qixin Wang , Muhammad Yasin , Mazhar Amjad Gilani , Asim Laeeq Khan , Linglong Shan , Xiangping Zhang

Achieving strong interaction with the targeted composition and constructing abundant transport channels is crucial to obtain the pervaporation (PV) membrane with high selectivity and flux. Here, three ionic liquids (ILs) were screened out based on their relative selectivity and capacity targeting for bioethanol dehydration by COSMO-RS. The interaction energies analysis between ILs, EtOH, and H₂O suggests that the ILs can form strong hydrogen bonds with water and disrupt the hydrogen bond in the EtOH–H₂O azeotropic mixture, which is beneficial for improving the selectivity. Furthermore, driven by the multiple hydrogen bonds, electrostatic interactions, and van der Waals forces, ILs could self-assemble with polyvinyl alcohol (PVA) to fabricate the PV membrane with well-ordered micelle nanostructure, as its structure was revealed by MD simulations. The formation of the ILs-PVA micelle dramatically influenced membrane surface morphology, roughness, and water contact angle, providing an extra transport channel for the membrane. The optimal membrane (at the cmc point) exhibited a superior ethanol dehydration separation factor of 1627, along with a flux of 684 g/m²h at 50 °C. It can be expected that this novel self-assembled ILs-PVA micelle nanostructure strategy will find promising applications in other azeotropic mixture separation processes, like ethanol-ethyl acetate, water-butanol, etc.

要获得具有高选择性和高通量的渗透蒸发（PV）膜，与目标成分实现强相互作用并构建丰富的传输通道至关重要。在此，利用 COSMO-RS 根据生物乙醇脱水的相对选择性和容量目标筛选出三种离子液体（ILs）。离子液体、EtOH 和 H2O 之间的相互作用能分析表明，离子液体能与水形成强氢键，并能破坏 EtOH-H2O 共沸混合物中的氢键，这有利于提高选择性。此外，在多重氢键、静电作用和范德华力的驱动下，ILs 能与聚乙烯醇（PVA）自组装，制造出具有有序胶束纳米结构的光伏膜，其结构已被 MD 模拟所揭示。ILs-PVA 胶束的形成极大地影响了膜的表面形态、粗糙度和水接触角，为膜提供了额外的传输通道。最佳膜（cmc 点）的乙醇脱水分离系数高达 1627，50 °C 时的通量为 684 g/m2h。可以预见，这种新型自组装 ILs-PVA 胶束纳米结构策略将在乙醇-乙酸乙酯、水-丁醇等其他共沸混合物分离过程中找到广阔的应用前景。

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引用次数: 0

Emerging contaminants removal through fluorine-doped carbon hollow fiber microfiltration membrane based on metal-free electro-Fenton 基于无金属电-芬顿的掺氟碳中空纤维微滤膜去除新出现的污染物

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-04 DOI: 10.1016/j.memsci.2024.123477

Yue Yang, Zhongcheng Yang, Xiong Liu, Lanyue Qi, Yujun Zhou, Zhigao Zhu, Junwen Qi, Jiansheng Li

The emerging contaminants with high toxicity and bioaccumulation potentially threaten to human health, which was difficult removed by traditional biological treatment or membrane separation. In view of this, a novel type of fluorine (F)-doped carbon hollow fiber microfiltration membrane was prepared for realizing emerging contaminants removal through metal-free electro-Fenton. Herein, polyaniline (PANI) was used as a precursor for preparation of porous carbon membrane. The graphitic N and pyridinic N on porous carbon were used as the active sites for H₂O₂ production and its further activation to ·OH, which realized metal-free electro-Fenton reaction. According to the results, the carbon nanotubes with F-PANI at the ratio of 1:1 and calcination temperature at 300 °C endowed the membrane moderate resistance and pure water permeability of 430 Ω and 48.51 L/(m² h bar), respectively. Importantly, the intensity of ·OH generation was further significant enhanced by introducing C–F bonding into the membrane. Therefore, the bisphenol A (BPA), sulfamethoxazole (SMZ) and atrazine (ATZ) removal rates were 92.63 %, 38.47 % and 27.05 %, respectively. For control group without bias, the removal rates of above contaminants were 0 % removal rates. Moreover, the membrane permeate loss by filtrating BPA, SMZ and ATZ were 0.13, 0.15 and 0.05, which were 0.20, 0.24 and 0.21 for control group.

高毒性、高生物蓄积性的新兴污染物对人类健康构成了潜在威胁，传统的生物处理或膜分离很难去除这些污染物。有鉴于此，本研究制备了一种新型氟（F）掺杂碳中空纤维微滤膜，通过无金属电-芬顿实现对新兴污染物的去除。在这里，聚苯胺（PANI）被用作制备多孔碳膜的前体。多孔碳上的石墨化氮和吡啶化氮被用作产生 H2O2 的活性位点，并进一步活化为 -OH，从而实现了无金属电-芬顿反应。结果表明，碳纳米管与 F-PANI 的比例为 1:1，煅烧温度为 300 ℃，膜的中等阻力和纯水渗透率分别为 430 Ω 和 48.51 L/(m2 h bar)。重要的是，在膜中引入 C-F 键后，-OH 的生成强度进一步显著增强。因此，双酚 A（BPA）、磺胺甲噁唑（SMZ）和阿特拉津（ATZ）的去除率分别为 92.63 %、38.47 % 和 27.05 %。无偏差对照组对上述污染物的去除率为 0%。此外，过滤双酚 A、SMZ 和 ATZ 的膜渗透损失分别为 0.13、0.15 和 0.05，而对照组分别为 0.20、0.24 和 0.21。

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引用次数: 0

Enhancing permeability of CA/MoS2 pervaporation membrane via electric field-induced orientation of MoS2 nanosheets 通过电场诱导 MoS2 纳米片的取向提高 CA/MoS2 渗透膜的渗透性

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-04 DOI: 10.1016/j.memsci.2024.123478

Jennifer Runhong Du , Jingfeng Zheng , Kailai Ma , Dechen Zhou , Chunliang Du

The formation of a mixed matrix membrane by incorporating nanofillers into a polymer matrix is a potential strategy to improve the separation performance of polymer membranes. However, agglomeration and random arrangement of nanofillers in the mixed matrix membrane result in lower permeation flux increase than expected. In this work, mixed matrix membranes composed of cellulose acetate polymer and varying amounts of Molybdenum disulfide (MoS₂) nanosheets as nanofillers were prepared, and an electric field was applied to induce the alignment of MoS₂ nanosheets in the membrane thickness direction. The effects of solution parameters including solvent type, MoS₂ content, and polymer concentration as well as electric field parameters i.e., frequency, strength, and action time on MoS₂ orientation were investigated using a stereoscopic microscope. The pervaporation desalination performance of mixed matrix membranes with randomly arranged MoS₂ and orientally arranged MoS₂ was assessed. At 2 wt% MoS₂ content, the mixed matrix membrane with orientally arranged MoS₂ exhibited a flux of 5.44 kg/(m²·h), representing a 25.9 % increase over the mixed matrix membrane with randomly arranged MoS₂, while maintaining a salt rejection rate of over 99.9 %. The mixed matrix membrane demonstrated good long-term stability with consistent water flux and salt rejection during 120 h of operation.

在聚合物基质中加入纳米填料形成混合基质膜，是提高聚合物膜分离性能的一种潜在策略。然而，纳米填料在混合基质膜中的团聚和随机排列会导致渗透通量的增加低于预期。在这项工作中，制备了由醋酸纤维素聚合物和不同量的二硫化钼（MoS2）纳米片作为纳米填料组成的混合基质膜，并施加电场诱导 MoS2 纳米片在膜厚度方向上排列。使用立体显微镜研究了溶液参数（包括溶剂类型、MoS2 含量和聚合物浓度）以及电场参数（即频率、强度和作用时间）对 MoS2 取向的影响。评估了随机排列 MoS2 和定向排列 MoS2 的混合基质膜的渗透淡化性能。在 MoS2 含量为 2 wt% 时，定向排列 MoS2 的混合基质膜的通量为 5.44 kg/（m2-h），比随机排列 MoS2 的混合基质膜提高了 25.9%，同时保持了超过 99.9% 的盐排斥率。在 120 小时的运行过程中，混合基质膜表现出良好的长期稳定性，水通量和盐分去除率保持一致。

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引用次数: 0

Highly flexible SCOF proton exchange membrane reinforced with PTFE to enhance fuel cell power density 用聚四氟乙烯增强的高柔性 SCOF 质子交换膜可提高燃料电池功率密度

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-04 DOI: 10.1016/j.memsci.2024.123479

Huimin Zhao , Bo Pang , Fujun Cui , Wanting Chen , Guihui Xie , Xuemei Wu , Ruishi Du , Chengbo Liu , Gaohong He

Sulfonated covalent organic frameworks (SCOFs) facilitate rapid proton conduction through densely ordered sulfonic acid groups, however, the brittleness of COFs self-supporting membranes often makes potential difficulty in fuel cell assembly and limits their power density. Herein, a highly flexible SCOF proton exchange membrane is developed through in-situ growth of a continuous BD(SO₃H)₂–COF microphase within porous PTFE networks. The strong hydrogen bonding between PTFE and BD(SO₃H)₂–COF contributes to the defect-free morphology of the BD(SO₃H)₂/PTFE membrane. The reinforce of PTFE network makes the membrane extremely high flexibility, achieving an elongation at break of 124.4 % even with a remarkably high SCOF mass proportion of 90 wt% (BD(SO₃H)₂/PTFE-0.9). This allows the membrane to be folded repeatedly, even in dry state. The swelling ratio in water at 80 °C is effectively restricted to 8.6 %, even with a high ion exchange capacity of 3.6 mmol g⁻¹ and a water uptake of 68.2 %. The densely ordered sulfonic acid groups in continuous BD(SO₃H)₂–COF microphase contribute to a high proton conductivity up to 249.2 mSꞏcm⁻¹ at 80 °C, approximately 1.5 folds that of Nafion 212. As a result, the BD(SO₃H)₂/PTFE-0.9 membrane achieves a fuel cell power density of 1195.3 mWꞏcm⁻² at 80 °C, along with a high open circuit voltage of 1.01 V, surpassing the-state-of-the-art COF-based proton exchange membranes. This work provides a novel strategy to fabricate COFs into flexible and size scalable membranes, enhancing the performance of fuel cells.

磺化共价有机框架（SCOFs）通过密集有序的磺酸基团促进质子快速传导，然而 COFs 自支撑膜的脆性往往给燃料电池组装带来潜在困难，并限制了其功率密度。本文通过在多孔聚四氟乙烯网络中原位生长连续的 BD(SO3H)2-COF 微相，开发出一种高柔性 SCOF 质子交换膜。聚四氟乙烯和 BD(SO3H)2-COF 之间的强氢键促成了 BD(SO3H)2/PTFE 膜的无缺陷形态。聚四氟乙烯网络的加强使膜具有极高的柔韧性，即使 SCOF 的质量比例高达 90 wt%（BD(SO3H)2/PTFE-0.9），断裂伸长率也能达到 124.4%。这使得膜即使在干燥状态下也能反复折叠。即使在离子交换容量高达 3.6 mmol g-1 和吸水率高达 68.2 % 的情况下，80 °C 时在水中的膨胀率也被有效限制在 8.6 %。连续 BD(SO3H)2-COF 微相中密集有序的磺酸基团使得质子电导率在 80 °C 时高达 249.2 mSꞏcm-1，约为 Nafion 212 的 1.5 倍。因此，BD(SO3H)2/PTFE-0.9 膜在 80 °C 时的燃料电池功率密度达到 1195.3 mWꞏcm-2，开路电压高达 1.01 V，超过了最先进的基于 COF 的质子交换膜。这项研究为将 COF 制成灵活、尺寸可扩展的膜提供了一种新策略，从而提高了燃料电池的性能。

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引用次数: 0

“Network-trapped engineering” of graphene oxide membrane with stable structure "结构稳定的氧化石墨烯膜 "网络陷阱工程

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-01 DOI: 10.1016/j.memsci.2024.123473

Yi Huang , Yu Qiang , Ruobing Yi , Shuai Wang , Shanshan Liang , Liang Chen

Graphene oxide (GO) membranes are considered ideal candidates for efficient water treatment due to their unique two-dimensional structure and excellent sieving properties. However, the swelling of graphene oxide in aqueous solutions makes it still challenging for practical application. Inspired by the spider web, in this work, we developed a “network-trapped engineering” strategy to stabilize the interlayer spacings of GO membranes, which are defined as GS-Sr membranes. The sodium alginate (SA) and Sr²⁺ were successfully fixed as the “network” and “rivets” in-between the GO nanosheets, respectively. Benefiting from the design of the network structure, the GS-Sr membranes exhibited excellent interlayer spacing stability. Meanwhile, this evenly distributed network structure in the GO laminates can further optimize the stacking of nanosheets, forming more orderly 2D confined nanochannels. As a result, the membranes exhibited superior salt/dye sieving performance, with a separation factor up to 179.13 for Na₂SO₄/CR, while still maintaining an outstanding water permeance of 70.14 L m⁻² h⁻¹ bar⁻¹. Furthermore, the GS-Sr membrane demonstrated stable separation performance in the long-term test, and the mechanical stability has also been enhanced in the mechanical test. Overall, compared with traditional simple cross-linking strategies, this strategy offers a new insight into fine-construction of two-dimensional nanochannels.

氧化石墨烯（GO）膜因其独特的二维结构和优异的筛分性能，被认为是高效水处理的理想候选材料。然而，氧化石墨烯在水溶液中的膨胀性使其在实际应用中仍面临挑战。受蜘蛛网的启发，在这项工作中，我们开发了一种 "网络陷阱工程 "策略来稳定 GO 膜的层间间距，并将其定义为 GS-Sr 膜。海藻酸钠（SA）和 Sr2+ 分别作为 "网络 "和 "铆钉 "被成功固定在 GO 纳米片之间。得益于网络结构的设计，GS-Sr 膜表现出优异的层间间距稳定性。同时，GO 薄片中这种均匀分布的网络结构可以进一步优化纳米片的堆叠，形成更有序的二维封闭纳米通道。因此，这种膜具有优异的盐分/染料筛分性能，Na2SO4/CR 的分离因子高达 179.13，同时还能保持 70.14 L m-2 h-1 bar-1 的出色透水性。此外，GS-Sr 膜在长期测试中表现出稳定的分离性能，在机械测试中的机械稳定性也有所提高。总之，与传统的简单交联策略相比，这种策略为二维纳米通道的精细构建提供了新的视角。

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引用次数: 0

Post-synthetic modification of MOF UiO-66-NH₂ membranes for efficient methanol/organic separation 对 MOF UiO-66-NH₂ 膜进行后合成修饰以实现高效甲醇/有机物分离

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-01 DOI: 10.1016/j.memsci.2024.123475

Langhui Wu , Ye Liang , Bo Zhang , Shenzhen Cong , Shenyi Tang , Kangkang Jiang , Liping Luan , Zhi Wang , Xinlei Liu

The separation of MeOH/organic mixtures poses a significant challenge in the chemical industry. In this study, metal-organic framework UiO-66-NH₂ membranes prepared by a secondary solvothermal method were employed for MeOH/DMC, MeOH/Tol and MeOH/MTBE separation. The membrane performance was significantly boosted by post-synthetic modification with oxalyl chloride (OC), succinyl chloride (SC), and salicylaldehyde (SA). The modified UiO-66-NH₂-OC and UiO-66-NH₂-SC membranes displayed simultaneous improvement of the separation factors and MeOH fluxes. The modified UiO-66-NH₂-SA membranes exhibited an order of magnitude enhancement of separation factors, with comparable MeOH fluxes. Specifically, separation factors of 3220 and 28,000 with MeOH fluxes of 1.18 kg m⁻² h⁻¹and 1.03 kg m⁻² h⁻¹ for 5/95 wt% MeOH/Tol and 5/95 wt% MeOH/MTBE separation at 40 °C, respectively, were delivered by UiO-66-NH₂-SA membranes. Moreover, the UiO-66-NH₂-SA membranes demonstrated good stability over 120 h's evaluation. This study offers a promising post-synthetic approach and a class of membrane materials for efficient MeOH/organic separation.

在化学工业中，MeOH/有机混合物的分离是一项重大挑战。本研究采用二次溶热法制备了金属有机框架 UiO-66-NH2 膜，用于分离 MeOH/DMC、MeOH/Tol 和 MeOH/MTBE。通过草酰氯（OC）、丁二酸酰氯（SC）和水杨醛（SA）进行合成后改性，膜的性能得到了显著提高。改性后的 UiO-66-NH2-OC 和 UiO-66-NH2-SC 膜同时提高了分离因子和 MeOH 通量。改性 UiO-66-NH2-SA 膜的分离因数提高了一个数量级，MeOH 通量与之相当。具体来说，UiO-66-NH2-SA 膜在 40 °C 下分离 5/95 wt% MeOH/Tol 和 5/95 wt% MeOH/MTBE 时，分离因子分别为 3220 和 28000，MeOH 通量分别为 1.18 kg m-2 h-1 和 1.03 kg m-2 h-1。此外，UiO-66-NH2-SA 膜在 120 小时的评估中表现出良好的稳定性。这项研究为高效分离甲醇/有机物提供了一种前景广阔的后合成方法和一类膜材料。

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引用次数: 0

Synergistic manipulation of the polymorphic structure and hydrophilicity of PVDF membranes based on the in-situ esterification reaction to prepare anti-fouling PVDF membranes 基于原位酯化反应协同操纵聚偏二氟乙烯膜的多态结构和亲水性以制备防污聚偏二氟乙烯膜

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-11-01 DOI: 10.1016/j.memsci.2024.123474

Xiao Kong , Qi-Zheng Wang , Ye-Fei Wang , Hao-Ming Huo , Fang-Qi Kou , Shu-Bo Zhang , Jun Zhao , Dan Zhang , Liang Hao , Yan-Jiao Chang , Dong-En Zhang

Improving the content of polar crystal phase and the hydrophilicity of PVDF membranes are proved the efficient ways to improve the enduringly anti-fouling ability of PVDF membranes. But synergistic manipulating the polymorphic structure and hydrophilicity of PVDF membranes is rarely reported so far. In this paper, the in-situ esterification reaction between styrene-maleic anhydride (SMA) and meglumine (MG) during nonsolvent induced phase separation (NIPS) process is found to simultaneously manipulate the polymorphic structure and hydrophilicity of PVDF membranes. The water contact angle of membranes is largely reduced from 95.8° to 31.2° with the increase in the MG adding amounts, proving that the hydrophilicity of PVDF membranes is notably improved. Moreover, the β-phase content is improved as the MG adding amounts increase due to the enhanced interactions between the –OH groups and the –CF₂ groups of PVDF through hydrogen bonds. As a result, a highly hydrophilic PVDF membrane with >90 % β-phase content is obtained. The durable antifouling testing reveals that the PVDF blend membranes possess lower flow decline ratio and higher flux recovery ratio compared with the virgin PVDF membranes, thus exhibiting better antifouling ability. The synergistic manipulation of hydrophilicity and crystalline phase of PVDF membranes might offer a paradigm shift in the design of high-performance separation membranes.

事实证明，提高 PVDF 膜的极性晶相含量和亲水性是提高 PVDF 膜持久抗污能力的有效途径。但协同操作 PVDF 膜的多晶态结构和亲水性迄今鲜有报道。本文发现，在非溶剂诱导相分离（NIPS）过程中，苯乙烯-马来酸酐（SMA）与甲基鲁胺（MG）之间的原位酯化反应可同时操纵 PVDF 膜的多晶结构和亲水性。随着 MG 添加量的增加，膜的水接触角从 95.8° 大大降低到 31.2°，这证明 PVDF 膜的亲水性得到了显著改善。此外，由于 PVDF 的 -OH 基团和 -CF2 基团之间通过氢键增强了相互作用，随着 MG 添加量的增加，β 相含量也得到了提高。因此，得到的高亲水性 PVDF 膜的β相含量为 90%。持久的防污测试表明，与原始 PVDF 膜相比，PVDF 混合膜具有更低的流量下降率和更高的流量恢复率，从而表现出更好的防污能力。对 PVDF 膜的亲水性和结晶相进行协同操作，可能会为高性能分离膜的设计提供一种范式转变。

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引用次数: 0

Aryl-ether-free polyphenylene-based anion exchange membranes incorporating N-cyclic quaternary ammoniums for enhanced alkaline fuel cell performance 不含芳基醚的聚苯乙烯基阴离子交换膜与 N-环季铵结合，可提高碱性燃料电池的性能

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-31 DOI: 10.1016/j.memsci.2024.123455

Xiaomeng Chu , Haoxi Zhang , Cuizhi Zhang , Runan Shao , Zitong Huang , Hongfu Lv , Shaojie Liu , Lei Liu , Nanwen Li , Song Zhao

Selecting appropriate polymer backbones is crucial for the advancement of anion exchange membranes (AEMs) that exhibit both high ionic conductivity and robust chemical stability. In this study, we synthesized rigid and chemically inert aryl-ether-free polyphenylene-based polymer backbones containing alkaline-resistant N-cyclic cations, i.e. dimethyl piperidinium (DMP) or 6-azonia-spiro[5.5]undecane (ASU), as high-performance AEMs. The procedure encompassed several key steps: superacid-catalyzed Friedel-Crafts polycondensation, bromomethylation, azidation, and Cu(I)-mediated azide-alkyne cycloaddition. The synthesized BP-ASU(DMP)-x copolymers demonstrated excellent film-forming capabilities to afford robust AEMs as compared to polyolefin-based counterparts. Owing to the significant incompatibility between the hydrophobic backbones and the hydrophilic cations, the BP-ASU(DMP)-x membranes exhibited a well-defined microphase-separated morphology, resulting in exceptionally high hydroxide conductivity, up to 157.2 mS cm⁻¹ at 80 °C in water. More importantly, BP-ASU-150 membrane exhibited no chemical degradation and a conductivity retention of >97 % when immersed in 1 M NaOH solution at 80 °C for 4000 h. Compared to the poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and polyolefin-based counterparts, the achieved outstanding alkaline stability is related to aryl-ether-free polyphenylene and alkali-stable N-cyclic cations, highlighting the importance of polymer backbones for AEM materials. Finally, all the polyphenylene-based AEMs with incorporated N-cyclic cations were assembled in single H₂/O₂ AEMFCs, with the BP-ASU-150 membrane demonstrating a peak power density (PPD) of 860.4 mW cm⁻² at a current density of 1363 mA cm⁻². We concluded that the BP-ASU(DMP) AEMs demonstrated superior performance across various metrics due to exceptional stability and robustness of polyphenylene polymers, highlighting their potential as backbones for high-performance AEM materials.

选择合适的聚合物骨架对于开发具有高离子传导性和强大化学稳定性的阴离子交换膜（AEM）至关重要。在本研究中，我们合成了含有耐碱 N 环阳离子（即二甲基哌啶鎓（DMP）或 6-氮杂螺[5.5]十一烷（ASU））的刚性和化学惰性无芳基聚苯乙烯基聚合物骨架，作为高性能 AEM。该过程包括几个关键步骤：超酸催化弗里德尔-卡夫斯缩聚、溴甲基化、叠氮化和 Cu(I)-mediated 叠氮-炔环化。与基于聚烯烃的共聚物相比，合成的 BP-ASU(DMP)-x 共聚物具有出色的成膜能力，可提供坚固耐用的 AEM。由于疏水性骨架与亲水性阳离子之间存在明显的不相容性，BP-ASU(DMP)-x 膜呈现出清晰的微相分离形态，因此具有极高的氢氧化物电导率，在 80 °C 的水中可达 157.2 mS cm-1。更重要的是，BP-ASU-150 膜在 80 °C 的 1 M NaOH 溶液中浸泡 4000 小时后，没有发生化学降解，电导率保持率高达 97%。与聚(2,6-二甲基-1,4-苯基氧化物)（PPO）和聚烯烃基同类产品相比，BP-ASU-150 所具有的出色碱性稳定性与不含芳基醚的聚亚苯基和碱性稳定的 N-环阳离子有关，凸显了聚合物骨架对 AEM 材料的重要性。最后，在单个 H2/O2 AEMFC 中组装了所有含有 N 环阳离子的聚苯基 AEM，其中 BP-ASU-150 膜在电流密度为 1363 mA cm-2 时的峰值功率密度（PPD）为 860.4 mW cm-2。我们得出的结论是，BP-ASU(DMP) AEM 在各种指标上都表现出了卓越的性能，这归功于聚苯聚合物卓越的稳定性和坚固性，凸显了它们作为高性能 AEM 材料骨架的潜力。

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引用次数: 0

Compromise mechanism of proton transfer in crown ether-based biomimetic proton exchange membranes: Insights from molecular dynamics simulations 基于冠醚的仿生物质子交换膜中质子传递的妥协机制：分子动力学模拟的启示

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-29 DOI: 10.1016/j.memsci.2024.123456

Yumei Zhao , Qingwei Gao , Xiaofei Xu , Chunyan Ma , Qikuan He , Yulin Min , Shuangliang Zhao

Proton exchange membrane fuel cells (PEMFCs) have emerged as a key research area due to their ability to convert various gaseous energy sources (such as hydrogen and methanol) into electrical energy with high efficiency and zero pollution. The design of the proton exchange membrane (PEM), which is the site for proton transfer, is critical. To explore the influence of characteristic functional groups on proton transfer mechanism in biomimetic proton exchange membranes, the crown ether structure was introduced into polymer backbone chains to mimic biological ion channels. The motion behaviors of proton were qualitatively characterized through molecular dynamics simulation. It was found that protons are strongest complexed in the best matching 18CO6-PEM case based on the analysis of RDF, residence time, interaction energy, and number of hydrogen bonds. The characteristic groups of biological proton channels with smaller or larger pores can help protons detach from the complexation under the action of an electric field. The proton transfer in crown-ether biomimetic proton exchange membranes is not just a single mechanism, but a compromise between two mechanisms in parallel. This work provides a new perspective on designing proton conduction membranes by embedding large ring motifs with intrinsic cavities and the key parameters required for establishing the proton transfer model.

质子交换膜燃料电池（PEMFC）能够将各种气态能源（如氢气和甲醇）高效、零污染地转化为电能，因此已成为一个重要的研究领域。质子交换膜（PEM）是质子传递的场所，其设计至关重要。为了探索特征官能团对仿生质子交换膜中质子传输机制的影响，研究人员在聚合物骨架链中引入了冠醚结构，以模拟生物离子通道。通过分子动力学模拟对质子的运动行为进行了定性分析。根据对 RDF、停留时间、相互作用能和氢键数量的分析，发现质子在最佳匹配的 18CO6-PEM 情况下复合能力最强。生物质子通道的特征基团具有较小或较大的孔隙，在电场作用下有助于质子脱离络合物。冠醚生物仿生质子交换膜中的质子传输并非只有一种机制，而是两种机制并行的折衷。这项工作为通过嵌入具有内在空腔的大环图案来设计质子传导膜提供了一个新的视角，并为建立质子传输模型提供了所需的关键参数。

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引用次数: 0

Ultra-low voltage modulated water-selective permeation for on-demand separation of oil/water emulsions based on the facilely prepared laminar membranes with high conductivity 基于简便制备的高导电性层流膜，按需分离油/水乳剂的超低电压调制水选择渗透技术

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2024-10-28 DOI: 10.1016/j.memsci.2024.123461

Song Song , Tianwen Wang , Jiaxiang Xia , Shiwen Bao , Xuexiao Hu , Wenjing Han , Yingzhuo Ma , Kunyan Sui , Jun Gao , Xueli Liu , Lei Jiang

Smart membranes with stimuli-modulated liquid-selective permeation hold promise for on-demand separation of oil/water mixtures, yet the facile preparation of membranes with sensitive and easily implemented responsiveness still remains a challenge. Herein, we present the sensitive manipulation of water-selective permeation using a weak electric field with ultra-low voltages and the resulting on-demand separation of oil-in-water emulsions on a facilely prepared laminar membrane. Fabricated via simple vacuum filtration, the MXene membrane possesses high conductivity and molecule-scaled transport channels, both of which facilitate the sensitive modulation. A voltage of just several negative volts (−4 V) can significantly switch the wetting and permeation of water on the membrane, which is distinctly lower than that previously reported (hundreds of volts and even several kV). In addition, the negatively charged membrane, under the applied bias, enhances the rejection of surfactant-wrapped oil droplets, preventing the fouling of material surfaces. Consequently, the separation of oil-in-water emulsions was achieved with high oil rejection rate (99 %) and considerable flux for a variety of oil types and percentages. Particularly for the crude oil/water mixtures, the rejection rate reached 99 % and the flux achieved 69.72 L m⁻² h⁻¹. This study presents a novel example for achieving easy and economical smart separation of oil/water mixtures using highly conductive materials, and should also spark research in areas such as water purification, drug delivery, microfluidic valves, etc.

具有刺激调制液体选择渗透性的智能膜有望实现油水混合物的按需分离，但如何轻松制备灵敏且易于实现响应的膜仍是一项挑战。在本文中，我们介绍了利用超低电压的弱电场灵敏操纵水选择性渗透，并由此在简易制备的层状膜上实现了水包油乳液的按需分离。MXene 膜通过简单的真空过滤制成，具有高导电性和分子尺度的传输通道，这两点都有助于实现灵敏的调制。仅几负伏（-4 V）的电压就能显著改变水在膜上的润湿和渗透，这明显低于之前报道的电压（几百伏甚至几千伏）。此外，带负电荷的膜在外加偏压的作用下，能增强对表面活性剂包裹的油滴的排斥，防止材料表面结垢。因此，在分离水包油型乳状液时，对各种油的类型和比例都能达到很高的油排斥率（99%）和相当大的通量。特别是对于原油/水混合物，其排油率达到 99%，通量达到 69.72 L m-2 h-1。这项研究为利用高导电性材料实现油/水混合物的简便、经济的智能分离提供了一个新的范例，也将为水净化、药物输送、微流体阀门等领域的研究带来启发。

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引用次数: 0