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Superacid catalyzed triptycene-based polymer to enhance membrane permeability for molecular sieving of nitrogen over VOC 超酸催化的三庚烯基聚合物可提高用于挥发性有机化合物氮分子筛分的膜渗透性
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100099
Yuan Gao , Zhihao Huang , Wenyue Lv , Hua Zhang , Yuanqing Ye , Rongfei Zhou , Huiyun Liao , Haoli Zhou , Wanqin Jin

Superacid catalysis, a suitable method for the synthesis of membrane materials owing to its facile polymerization procedure, has been extensively studied. However, superacid-catalyzed binary coplanar polymer membranes generally exhibit low permeabilities. In this study, a rigid 3D triptycene-based polymer was synthesized by the superacid catalysis of triptycene with trifluoroacetophenone and diphenyl ether to enhance membrane permeability for the molecular sieving of nitrogen over volatile organic compound (VOC). The synthesis of polymers with (CF3PhET) or without triptycene (CF3PhE) was investigated using different characterizations. The triptycene content of the synthesized polymers was optimized based on an analysis of the molecular weight, membrane-forming properties, and separation performance. The separation performances of membranes fabricated using CF3PhE, CF3PhET, and a mixture of CF3PhE and triptycene were compared. Results showed that the introduction of non-coplanar triptycene in the membrane can increase permeability by nearly 60 times due to the enhanced free volume, from 30 Barrer for the CF3PhE membrane to 1755 Barrer for the membrane with 5 ​mol% triptycene content for the separation of a 3 ​mol% nitrogen/cyclohexane mixture at 1 ​L/(m2·min). Furthermore, the rejection remains constant, which provides an effective idea for the synthesis of membrane materials with high performance using superacid catalysis.

超酸催化因其简便的聚合程序而成为合成膜材料的一种合适方法,已被广泛研究。然而,超酸催化的二元共面聚合物膜通常表现出较低的渗透性。在本研究中,通过三氟苯乙酮和二苯醚对三庚烯进行超酸催化,合成了一种刚性三维三庚烯基聚合物,以提高挥发性有机化合物(VOC)分子筛氮的膜渗透性。利用不同的特性研究了含有(CF3PhET)或不含三庚烯(CF3PhE)的聚合物的合成。根据对分子量、成膜性能和分离性能的分析,对合成聚合物中的三庚烯含量进行了优化。比较了使用 CF3PhE、CF3PhET 以及 CF3PhE 和三庚烯混合物制造的膜的分离性能。结果表明,在 1 升/(平方米/分钟)的条件下分离 3 摩尔%的氮气/环己烷混合物时,在膜中引入非共面三庚烯可使自由体积增大,从而使渗透性提高近 60 倍,从 CF3PhE 膜的 30 巴勒提高到三庚烯含量为 5 摩尔%的膜的 1755 巴勒。此外,排斥率保持不变,这为利用超酸催化合成高性能膜材料提供了有效的思路。
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引用次数: 0
One-dimensional Fe/C constructed Janus membrane enables highly-efficient and stable solar-driven interfacial evaporation 一维 Fe/C 构建的 Janus 膜可实现高效稳定的太阳能驱动界面蒸发
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100108
Junqi Ning , Cailin Yang , Qiuyu Mei , Limingming Huang , Kai Han
The practical use of solar-driven interfacial evaporation is hampered by high cost, low photothermal conversion efficiency, and poor stability. Herein, a one-dimensional Fe/C constructed photothermal membrane is rationally developed to replace precious metals via the combination of Fe plasmon resonance with carbon molecular thermal vibration. The membrane exhibits excellent light absorbance (95.72 ​%) and water evaporation rate (2.60 ​kg ​m−2 ​h−1) leading to photothermal conversion efficiency up to 95.65 ​% under 1 sun illumination. Janus Fe/C membrane with superhydrophobic and hydrophilic structure is further prepared by polydimethylsiloxane (PDMS) coating to improve long-term stability. The evaporation rate can be maintained at over 90 ​% after 80 ​h illumination for real seawater treatment with metal ion removal efficiency >99 ​%. It also shows high evaporation performance and stability for organic solvents such as IPA, and NMP. Thus, the 1D Fe/C constructed Janus membrane is a promising candidate for energy-saving solar-driven interfacial solvent evaporation including seawater desalination, wastewater treatment, and organic solvent purification.
太阳能驱动的界面蒸发因成本高、光热转换效率低和稳定性差而阻碍了其实际应用。在此,我们通过铁等离子体共振与碳分子热振动的结合,合理地开发了一种一维铁/碳构建的光热膜,以取代贵金属。该膜具有优异的光吸收率(95.72%)和水蒸发率(2.60 kg m-2 h-1),在太阳光照射下的光热转换效率高达 95.65%。通过聚二甲基硅氧烷(PDMS)涂层进一步制备了具有超疏水和亲水结构的 Janus Fe/C 膜,以提高其长期稳定性。在实际海水处理中,经过 80 小时光照后,蒸发率仍能保持在 90% 以上,金属离子去除率高达 99%。此外,它对 IPA 和 NMP 等有机溶剂也表现出较高的蒸发性能和稳定性。因此,一维 Fe/C 构建的 Janus 膜是太阳能驱动的节能界面溶剂蒸发(包括海水淡化、废水处理和有机溶剂提纯)的理想候选材料。
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引用次数: 0
One-step rejuvenation for prolonging running lifespan of nanofiltration membranes 延长纳滤膜运行寿命的一步再生法
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100094
Guoyuan Pan , Muhua Zhao , Ying Wan , Guoke Zhao , Hao Yu , Gongqing Tang , Yang Zhang , Yiqun Liu

Commercial nanofiltration (NF) membranes based on polyamides may experience a decline in permeation performance after prolonged operation. The short lifespan of NF membranes will lead to waste and additional carbon emissions. Thus, rejuvenating membranes and extending their lifespan seem more meaningful than investigating new materials. In this paper, polyamide NF membranes were modified with various polyphenol monomers to improve their permeation performance. The effects of different polyphenols on pore size, surface morphology, and permeation performance of the NF membranes were thoroughly investigated. After modification with tannic acid, the NF membrane exhibits improved salt rejection while experiencing an acceptable decrease in water flux. It should be noted that the commercial NF membrane element fabricated by Koch can recover its Na2SO4 rejection from 83.0% to 94.2% and demonstrate long-term stability after rejuvenation with tannic acid. Combined with the environmental friendliness of polyphenols, this straightforward modification method has the potential for prolonging the operational lifespan of industrial NF membrane products.

基于聚酰胺的商用纳滤膜在长时间运行后,渗透性能可能会下降。纳滤膜的短寿命将导致浪费和额外的碳排放。因此,使膜年轻化并延长其使用寿命似乎比研究新材料更有意义。本文用不同的多酚单体对聚酰胺 NF 膜进行改性,以提高其渗透性能。本文深入研究了不同多酚对 NF 膜孔径、表面形态和渗透性能的影响。经单宁酸改性后,NF 膜的盐排斥性能得到改善,同时水通量的下降幅度也在可接受范围内。值得注意的是,Koch 制造的商用 NF 膜元件的 Na2SO4 排盐率可从 83.0% 提高到 94.2%,并在使用单宁酸进行年轻化后表现出长期稳定性。结合多酚的环境友好性,这种简单的改性方法有望延长工业 NF 膜产品的运行寿命。
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引用次数: 0
Microporous and functional group Co-designed polyesteramide membranes for efficient and broad-spectrum organic solvent nanofiltration 用于高效和广谱有机溶剂纳滤的微孔和官能团协同设计聚酯酰胺膜
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100098
Zheng Liu , Yuxuan Sun , Heguo Han , Qifeng Zhang , Shenghai Li , Suobo Zhang

Organic solvent nanofiltration (OSN) is an emerging energy-efficient separations technology, which urgently requires easily processable OSN membranes with high selectivity and broad-spectrum organic solvent applicability to facilitate enhanced industrial applications. Herein, we describe the preparation of microporous polyesteramide (PEA) membranes through interfacial polymerization (IP) between amino-diphenol monomers and trimesoyl chloride (TMC) on a poly(ether ether ketone) (PEEK) support. The crosslinked network structures and large twisted monomers enhance the microporosity of PEA membranes, leading to a significant improvement in solvent permeance while maintaining high selectivity. The optimized PEA membrane demonstrates exceptional permeance for acetone (21.0 ​L ​m−2 ​h−1 bar−1) and methanol (14.3 ​L ​m−2 ​h−1·bar−1), with a molecular weight cut-off of 296 ​g ​mol−1. Additionally, the PEA/APH-diphenol membrane exhibits ultrafast permeance for the nonpolar solvent toluene (8.3 ​L ​m−2 ​h−1·bar−1), owing to the introduction of a large number of ester groups. Overall, PEA membranes prepared through the molecular-level structure design of IP monomers possess enormous industrial application potential owing to their high performance and broad-spectrum applications.

有机溶剂纳滤(OSN)是一种新兴的高能效分离技术,迫切需要具有高选择性和广谱有机溶剂适用性的易加工OSN膜,以促进工业应用。在此,我们介绍了通过氨基二苯酚单体与三甲基甲酰氯(TMC)在聚醚醚酮(PEEK)载体上的界面聚合(IP)制备微孔聚酯酰胺(PEA)膜的方法。交联网络结构和大扭曲单体提高了 PEA 膜的微孔率,从而在保持高选择性的同时显著改善了溶剂渗透性。优化后的 PEA 膜对丙酮(21.0 L m-2 h-1 bar-1)和甲醇(14.3 L m-2 h-1 bar-1)具有优异的渗透性,截留分子量为 296 g mol-1。此外,由于引入了大量酯基,PEA/APH-二苯酚膜对非极性溶剂甲苯(8.3 L m-2 h-1 bar-1)的渗透率超快。总之,通过对 IP 单体进行分子级结构设计而制备的 PEA 膜因其高性能和广谱应用而具有巨大的工业应用潜力。
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引用次数: 0
Design of high-performance electro-driven nanofiltration membrane via facile co-deposition of pyrogallol and polyethyleneimine for sustainable resource recovery from landfill leachate concentrate 通过焦耳酚和聚乙烯亚胺的简易共沉积设计高性能电驱动纳滤膜,实现垃圾填埋场渗滤液浓缩物的可持续资源回收
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100106
Jiale Du , Zijian Yu , Jiangjing Li , Shuangling Xie , Lianxin Chen , Jiuyang Lin
Conventional treatment methods of landfill leachate concentrate mainly focus on the degradation or removal of humic substance, which are prone to secondary pollution and fail to meet the requirements of current sustainable development. The key to sustainable management of landfill leachate concentrate is to precisely fractionate the existing humic substance and inorganic salts as individual resources. Here, electro-driven nanofiltration membranes were fabricated by sodium periodate inducing co-deposition of pyrogallol and polyethyleneimine on the loose polyamide-based nanofiltration substrate membranes as high-performance anion conducting membrane. The pyrogallol/polyethyleneimine composite coating layer endowed the electro-driven nanofiltration membranes with reduced surface negative charge and specific areal electric resistance for enhanced anion transfer. During the electro-driven nanofiltration process, the fabricated membrane with a 30-min co-deposition exhibited an extremely fast anion transfer rate and outstanding fractionation performance with 99.08 ​% humic substance recovery of 99.08 ​%. Particularly, the fabricated membrane showed stable separation capacity over an 8-cycle electro-driven nanofiltration operation, demonstrating a low fouling propensity. Our study sheds light on the strategy to fabricate high-performance electro-driven nanofiltration membranes via co-deposition of pyrogallol and polyethyleneimine, paving the way to sustainable treatment of landfill leachate concentrate.
垃圾填埋场渗滤液浓缩物的传统处理方法主要是降解或去除腐殖质,容易造成二次污染,不符合当前可持续发展的要求。垃圾填埋场渗滤液浓缩物可持续管理的关键是将现有的腐殖质和无机盐作为独立资源进行精确分馏。在此,我们利用高碘酸钠诱导焦聚糖醇和聚乙烯亚胺在疏松的聚酰胺基纳滤基底膜上共沉积,制备了电驱动纳滤膜,作为高性能阴离子传导膜。焦棓酚/聚乙烯亚胺复合涂层使电驱动纳滤膜的表面负电荷和比电阻降低,从而增强了阴离子传导能力。在电驱动纳滤过程中,经过 30 分钟共沉积的制备膜具有极快的阴离子转移速度和出色的分馏性能,腐殖质回收率高达 99.08%。特别是,所制备的膜在 8 个周期的电驱动纳滤操作中表现出稳定的分离能力,显示出较低的结垢倾向。我们的研究揭示了通过共沉积焦耳酚和聚乙烯亚胺来制造高性能电驱动纳滤膜的策略,为垃圾填埋场渗滤液浓缩物的可持续处理铺平了道路。
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引用次数: 0
A novel high temperature resistance thin film composite polyamide reverse osmosis membrane with covalent organic frameworks intermediate layer 带有共价有机框架中间层的新型耐高温薄膜复合聚酰胺反渗透膜
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100101
Xun Li , Chen-Jie Wei , Ni-Jie Liu , Nian Zhang , Sa-Ren Qi , Bo-Ming Xie , He-Lin Zhu , Xue-Li Cao , Li-Fen Liu

Both salt rejection and pressure-bearing properties of the conventional thin film composite (TFC) polyamide reverse osmosis (RO) membrane are easily weakened at high temperature. In order to improve the high temperature resistance, in this work, a polyamide TFC RO membrane with covalent organic frameworks (COFs) intermediate layer was prepared. Firstly, the COFs layer was decorated on polyether sulfone (PES) support membrane by a unidirectional diffusion method and further modified for shrinking the micropore via the chemical crosslinking reaction with 1,3-diamino-2-propanol (DAPL) or ethylenediamine (EDA), and then continued the conventional interfacial polymerization of m-phenylene diamine (MPD) and trimesoyl chloride (TMC) on the resultant COFs layer for preparing the RO membrane. Furthermore, the correlationship between the microstructure of COFs layer and the separation performance of modified RO membrane was systematically investigated. Due to the introduction of the COFTpPa-DAPL intermediate layer with more regular microstructure and specific hydrophilicity, the resultant TFC-COFTpPa-DAPL RO membrane exhibited improvement in water flux by 30 ​% (reached to 50.5 ​L ​m−2 ​h−1) and higher salt rejection (>99.5 ​%) as compared with the conventional polyamide RO membrane and other reported temperature resistance RO membranes. Meanwhile, this TFC-COFTpPa-DAPL membrane showed good long-term separation stability during the RO process for 160 ​h. Especially, its water flux increased to 98.8 ​L ​m−2 ​h−1 without weakening salt rejection (about 99.4 ​%) at 70 ​°C. This study provides an effective way to fabricate the high temperature resistance TFC polyamide RO membrane with good comprehensive separation performance based on COFs intermediate layer.

传统的薄膜复合(TFC)聚酰胺反渗透(RO)膜的拒盐和承压性能在高温下很容易被削弱。为了提高耐高温性能,本研究制备了一种带有共价有机框架(COFs)中间层的聚酰胺 TFC 反渗透膜。首先,采用单向扩散法在聚醚砜(PES)支撑膜上装饰 COFs 层,并通过与 1,3-二氨基-2-丙醇(DAPL)或乙二胺(EDA)的化学交联反应进一步修饰收缩微孔,然后在所得 COFs 层上继续进行间苯二胺(MPD)和三甲基甲酰氯(TMC)的常规界面聚合,制备出 RO 膜。此外,还系统研究了 COFs 层的微观结构与改性反渗透膜分离性能之间的相关性。与传统的聚酰胺反渗透膜和其他已报道的耐温反渗透膜相比,由于引入了具有更规整微观结构和特定亲水性的 COFTpPa-DAPL 中间层,所制备的 TFC-COFTpPa-DAPL 反渗透膜的水通量提高了 30%(达到 50.5 L m-2 h-1),盐排斥率更高(99.5%)。同时,这种 TFC-COFTpPa-DAPL 膜在反渗透过程中表现出良好的长期分离稳定性,持续时间长达 160 小时。特别是,在 70 °C条件下,其水通量增加到 98.8 L m-2 h-1,而盐排斥率(约 99.4 %)却没有降低。这项研究为基于 COFs 中间层制造具有良好综合分离性能的耐高温 TFC 聚酰胺反渗透膜提供了一种有效方法。
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引用次数: 0
Gas transport mechanisms through MOF glass membranes 通过 MOF 玻璃膜的气体输送机制
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100104
Huan Liu , Huanni Xia , Rui Yao , Jianqiao Hu , Lifeng Zhang , Hua Jin , Yanshuo Li

The study provides an in-depth study on the gas adsorption and transport behaviors of MOF glass membranes for the first time. Temperature dependance of gas permeability, adsorption coefficients and diffusion coefficients between 298 ​K and 313 ​K for TIF-4 and ZIF-62 glass membrane were evaluated. The CO2 permeability was dominated by the adsorption process, while CH4 transport was mainly driven by the activated diffusion. Further, the MOF glass membranes exhibited significant entropic selectivity in adsorption, along with notable enthalpic selectivity in diffusion.

该研究首次对 MOF 玻璃膜的气体吸附和传输行为进行了深入研究。研究评估了 TIF-4 和 ZIF-62 玻璃膜在 298 K 和 313 K 之间的气体渗透性、吸附系数和扩散系数的温度依赖性。二氧化碳的渗透性由吸附过程主导,而 CH4 的传输则主要由活化扩散驱动。此外,MOF 玻璃膜在吸附过程中表现出显著的熵选择性,而在扩散过程中则表现出明显的焓选择性。
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引用次数: 0
Three-dimensional covalent organic frameworks for advanced membrane separations 用于高级膜分离的三维共价有机框架
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100109
Kai Sheng , Junyong Zhu , Lei Ge , Jiale Du , Tingting Luo , Lei Jiang , Wenheng Jing , Shi-Peng Sun , Yatao Zhang , Bart Van der Bruggen
Three-dimensional covalent organic frameworks (3D COFs) have emerged as a promising class of crystalline materials due to large surface areas, interconnected porosity, and accessible active sites. Their structural versatility, enabled by the judicious selection of organic building blocks, allows for precise tuning of pore size, architecture, and functionality. These unique attributes position 3D COFs as ideal candidates for the development of tailored membrane materials capable of high-performance separations. This review provides a comprehensive overview of the synthesis methodologies and applications of 3D COF-based membranes. The critical role of their pore size, topology, stability, hydrophilicity/hydrophobicity and surface charge on membrane structure and performance is examined. In addition, various fabrication methods for 3D COF-based membranes (e.g., blending, in situ growth, and interfacial polymerization) are presented. The usage of 3D COF-based membranes in diverse fields such as gas separation, water treatment, organic solvent nanofiltration, pervaporation, and proton exchange is also outlined. The review concludes by identifying key challenges and outlining future research directions for advancing the field of 3D COF-based membranes.
三维共价有机框架(3D COFs)具有较大的表面积、相互连接的孔隙度和可访问的活性位点,因此已成为一类前景广阔的晶体材料。通过明智地选择有机结构单元,三维共价有机框架可实现对孔隙大小、结构和功能的精确调整,从而实现其结构的多样性。这些独特的属性使三维 COFs 成为开发能进行高性能分离的定制膜材料的理想候选材料。本综述全面概述了基于三维 COF 的膜的合成方法和应用。研究了孔径、拓扑结构、稳定性、亲水性/疏水性和表面电荷对膜结构和性能的关键作用。此外,还介绍了三维 COF 基膜的各种制造方法(如混合、原位生长和界面聚合)。还概述了三维 COF 基膜在气体分离、水处理、有机溶剂纳滤、渗透蒸发和质子交换等不同领域的应用。综述最后指出了推进三维 COF 基膜领域的关键挑战并概述了未来的研究方向。
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引用次数: 0
Novel PA/PVDF hollow fiber nanofiltration membrane with high permeability and Ca2+/antibiotics selectivity for drinking water purification 具有高渗透性和 Ca2+/抗生素选择性的新型 PA/PVDF 中空纤维纳滤膜用于饮用水净化
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100102
Yuanhui Tang , Jihao Zhu , Huifang Yu , Fanchen Zhang , Song Hu , Hedi Chen , Chunhui Zhang , Huanhuan Wu , Lixin Yu , Xiaolin Wang , Haihui Wang , Li Ding , Yakai Lin

Emerging contaminants, including antibiotics, threaten water safety and public health. To remove these contaminants while retaining beneficial minerals in water, such as calcium (Ca), a novel thin-film composite nanofiltration (NF) membrane was manufactured through polymerization of a barrier layer composed of polypiperazine amide onto polyvinylidene fluoride (PVDF) hollow fiber (HF) substrate. The pore size of the PVDF surface was refined by introducing poly(vinylpyrrolidone) via a thermally induced phase separation method. Then piperazine (PIP) and trimesoyl chloride were selected to synthesize the NF membrane by interfacial polymerization with NaHCO3 as an additive. The influence of PIP concentration on the membrane morphology and separation performance was investigated. The optimized HF NF membrane (NF3) exhibited high water permeability (8.08 ​L/(m2 ​h ​bar)) due to its strong hydrophilicity. It also demonstrated a molecular weight cut-off of 378 ​Da and an enhanced negative surface charge (−43.96 ​mV), which was beneficial for the exclusion of antibiotics and passage of Ca2+. The high tetracycline rejection (98.9 ​%) enabled the NF3 membrane to achieve superior Ca2+/antibiotic selectivity (37.27) compared with most commercially available NF membranes. This study offers novel insights into tailoring the mineral/micropollutant selectivity of HF NF membranes for drinking water purification.

包括抗生素在内的新兴污染物威胁着水安全和公众健康。为了在去除这些污染物的同时保留水中的有益矿物质,如钙(Ca),通过在聚偏二氟乙烯(PVDF)中空纤维(HF)基材上聚合由聚哌嗪酰胺组成的阻挡层,制造出了一种新型薄膜复合纳滤(NF)膜。通过热诱导相分离法引入聚乙烯吡咯烷酮,细化了 PVDF 表面的孔径。然后选择哌嗪(PIP)和三甲基甲酰氯,以 NaHCO3 为添加剂,通过界面聚合合成 NF 膜。研究了 PIP 浓度对膜形态和分离性能的影响。优化后的 HF NF 膜(NF3)由于具有较强的亲水性,因此具有较高的透水性(8.08 L/(m2 h bar))。它还显示出 378 Da 的分子量截止值和增强的负表面电荷(-43.96 mV),这有利于抗生素的排除和 Ca2+ 的通过。与大多数市售 NF 膜相比,NF3 膜对四环素的高排斥率(98.9%)使其具有更高的 Ca2+/抗生素选择性(37.27)。这项研究为定制用于饮用水净化的高频 NF 膜的矿物质/微污染物选择性提供了新的见解。
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引用次数: 0
Hydroxide exchange membranes towards water electrolysis and fuel cells: A review on the recent advances, challenges and opportunities
Pub Date : 2024-01-01 DOI: 10.1016/j.advmem.2024.100111
Wei Wang , Yunfei Sun , Xiaofen Liu , Ming Wei , Chenyi Zhao , Kai-Ge Zhou , Meiling Wu
Hydroxide exchange membranes (HEMs) featuring high-performance and low-cost have attracted numerous attention due to their potential in water electrolysis and fuel cell applications. The main challenges of their relatively low ionic conductivity and insufficient stability have been alleviated by the rapid advancements in the latest years, especially with the emerging new materials with fine regulation of ion transport channels and the molecular design of the nonvolatile HEM in the operation condition. This review provides a comprehensive overview of the latest advancements in HEMs, focusing on the mechanism, influencing factors, and mitigation approaches of ionic conductivity and stability. In particular, we systematically overview the importance and regulation approaches of ion transport channels, including the channel size, channel orientation, and newly emerging membranes with intrinsic channels. Moreover, the influences of the operation conditions in practical devices on the performance of HEM are also overviewed and discussed. By offering insights into the fundamental mechanism, design strategies of ion transport channel and polymer chemistry, discussion of the challenges of each material, and potential opportunities, this work will contribute to the development of advanced HEM for hydrogen-electricity conversion devices.
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引用次数: 0
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Advanced Membranes
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