Pub Date : 2024-11-17DOI: 10.1016/j.memsci.2024.123518
A.A. Lysova , A.D. Manin , D.V. Golubenko , I.I. Ponomarev , V.A. Altynov , N. Hilal , A.B. Yaroslavtsev
Ion exchange membranes with high monovalent ion selectivity are essential for extracting valuable components from natural and waste waters. One of the approaches to their fabrication is the creation of nanostructured materials with ion-conducting channels. In this study, materials based on cardo polybenzimidazole (PBI–O-PhT) containing Zn2+, Cr3+ and Cu2+ ions were obtained and used for the first time for electrodialysis separation. The formation of crosslinked structure due to metal-benzimidazole coordination bonds was demonstrated. The obtained metal-polymer membranes have ionic conductivity comparable to commercial ones, reaching 0.32 mS cm−1, and high values of nitrate ion transport numbers (99.2 %). It is shown that the obtained membranes achieve incredibly high values of selectivity coefficients for anion separation. The highest and most stable values were obtained for the copper-containing membrane PBI/Cu-50, which are P(NO3/SO4) = 729, P(Cl/SO4) = 109 and P(NO3/Cl) = 6.66.
{"title":"Ultra-high nitrate-selective metal-polymer membranes based on cardo polybenzimidazole for electrodialysis","authors":"A.A. Lysova , A.D. Manin , D.V. Golubenko , I.I. Ponomarev , V.A. Altynov , N. Hilal , A.B. Yaroslavtsev","doi":"10.1016/j.memsci.2024.123518","DOIUrl":"10.1016/j.memsci.2024.123518","url":null,"abstract":"<div><div>Ion exchange membranes with high monovalent ion selectivity are essential for extracting valuable components from natural and waste waters. One of the approaches to their fabrication is the creation of nanostructured materials with ion-conducting channels. In this study, materials based on cardo polybenzimidazole (PBI–O-PhT) containing Zn<sup>2+</sup>, Cr<sup>3+</sup> and Cu<sup>2+</sup> ions were obtained and used for the first time for electrodialysis separation. The formation of crosslinked structure due to metal-benzimidazole coordination bonds was demonstrated. The obtained metal-polymer membranes have ionic conductivity comparable to commercial ones, reaching 0.32 mS cm<sup>−1</sup>, and high values of nitrate ion transport numbers (99.2 %). It is shown that the obtained membranes achieve incredibly high values of selectivity coefficients for anion separation. The highest and most stable values were obtained for the copper-containing membrane PBI/Cu-50, which are P(NO<sub>3</sub>/SO<sub>4</sub>) = 729, P(Cl/SO<sub>4</sub>) = 109 and P(NO<sub>3</sub>/Cl) = 6.66.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123518"},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720901","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}
Prewetting-induced switchable wettability materials demonstrate considerable potential for a diverse range of applications in comparison to traditional oil-water separation membranes including conventional special wetting materials, due to the distinctive advantages they offer. The current prewetting-induced switchable wettability materials are still constrained by the preparation strategy, separation performance and stability in practical application environment. This study presents a method for the preparation of PEEK/PANI bi-functional oil-water separation membranes by electrospinning and in-situ polyaniline growth. The controllable in-situ growth of PANI particles on PEEK fibers resulted in the formation of surface nano-micro structures, which enhanced the switchable underwater oleophobicity and underoil hydrophobicity of the membrane. The switching of wettability and the separation process is induced by prewetting in water or oil. The membranes display high permeability (maximum water flux of up to 8910 L⋅m−2⋅h−1) and separation efficiency (greater than 99.9 %) in gravity-driven oil-water mixtures/emulsion separation. PEEK-PANI composite fiber membranes demonstrate consistent separation performance in a range of corrosive or organic solvent environments due to the robust nature of the materials and the structural wettability This work presents a novel approach for the introduction of surface nano-micro structures and switchable structural wettability, as well as the production of high-performance multifunctional oil-water separation materials.
{"title":"PEEK-PANI bi-functional oil-water separation membrane based on structural switchable wettability","authors":"Boqian Zhao, Ziyu Lin, Ruiyin Sun, Guannan Chen, Zhiwei Zhao, Wenying Li, Liyuan Chen, Yirong Sun, Jiadi Liu, Jinhui Pang, Zhenhua Jiang","doi":"10.1016/j.memsci.2024.123501","DOIUrl":"10.1016/j.memsci.2024.123501","url":null,"abstract":"<div><div>Prewetting-induced switchable wettability materials demonstrate considerable potential for a diverse range of applications in comparison to traditional oil-water separation membranes including conventional special wetting materials, due to the distinctive advantages they offer. The current prewetting-induced switchable wettability materials are still constrained by the preparation strategy, separation performance and stability in practical application environment. This study presents a method for the preparation of PEEK/PANI bi-functional oil-water separation membranes by electrospinning and in-situ polyaniline growth. The controllable in-situ growth of PANI particles on PEEK fibers resulted in the formation of surface nano-micro structures, which enhanced the switchable underwater oleophobicity and underoil hydrophobicity of the membrane. The switching of wettability and the separation process is induced by prewetting in water or oil. The membranes display high permeability (maximum water flux of up to 8910 L⋅m<sup>−2</sup>⋅h<sup>−1</sup>) and separation efficiency (greater than 99.9 %) in gravity-driven oil-water mixtures/emulsion separation. PEEK-PANI composite fiber membranes demonstrate consistent separation performance in a range of corrosive or organic solvent environments due to the robust nature of the materials and the structural wettability This work presents a novel approach for the introduction of surface nano-micro structures and switchable structural wettability, as well as the production of high-performance multifunctional oil-water separation materials.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123501"},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720776","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}
Pub Date : 2024-11-17DOI: 10.1016/j.memsci.2024.123515
Qiao Liu , Xiaotian Xia , Nong Xu , Qing Wang , Long Fan , Yinhua Wan
Achieving uniform dispersion of nanoparticles within the polymer membrane matrix while simultaneously constructing continuous selective permeation channels has always been key to preparing high-performance mixed matrix membranes. In this study, we employ glycerol (Gol) molecules as “bridges” to harness the hydrogen bonding interactions between Gol, TpHz, and poly(vinyl alcohol) (PVA) molecules. This approach facilitates the nanoscale dispersion of TpHz nanoparticles within the PVA membrane, establishing continuous channels that selectively permit the permeation of water molecules. By incorporating just 0.3 wt % of TpHz nanoparticles, the resultant PVA/Gol/TpHz membrane demonstrates a mechanism that favors the selective adsorption, dissolution, and rapid diffusion of water molecules from the feed, thereby reducing the activation energy required for their permeation through the membrane. The prepared PVA/Gol/TpHz membrane with pure water contact angle of only 19.6° has total flux and separation factor of 134 L m−2 h−1 and 705, which were 3.4 and 3.5 times higher than those of the pure PVA membrane, respectively. It broke the “trade-off” effect of traditional PVA membrane. Moreover, the tensile strength and thermal decomposition temperature of the PVA/Gol/TpHz membrane were increased from 130.31 MPa to 120.90 °C to 442.05 MPa and 246.8 °C, respectively. The membrane structure and separation performances remained stable during the 80-h pervaporation test, which suggests potential for industrial applications.
{"title":"Glycerol-assisted uniform dispersion of TpHz nanoparticles in the poly(vinyl alcohol) membrane matrix to construct water permeation channels","authors":"Qiao Liu , Xiaotian Xia , Nong Xu , Qing Wang , Long Fan , Yinhua Wan","doi":"10.1016/j.memsci.2024.123515","DOIUrl":"10.1016/j.memsci.2024.123515","url":null,"abstract":"<div><div>Achieving uniform dispersion of nanoparticles within the polymer membrane matrix while simultaneously constructing continuous selective permeation channels has always been key to preparing high-performance mixed matrix membranes. In this study, we employ glycerol (Gol) molecules as “bridges” to harness the hydrogen bonding interactions between Gol, TpHz, and poly(vinyl alcohol) (PVA) molecules. This approach facilitates the nanoscale dispersion of TpHz nanoparticles within the PVA membrane, establishing continuous channels that selectively permit the permeation of water molecules. By incorporating just 0.3 wt % of TpHz nanoparticles, the resultant PVA/Gol/TpHz membrane demonstrates a mechanism that favors the selective adsorption, dissolution, and rapid diffusion of water molecules from the feed, thereby reducing the activation energy required for their permeation through the membrane. The prepared PVA/Gol/TpHz membrane with pure water contact angle of only 19.6° has total flux and separation factor of 134 L m<sup>−2</sup> h<sup>−1</sup> and 705, which were 3.4 and 3.5 times higher than those of the pure PVA membrane, respectively. It broke the “trade-off” effect of traditional PVA membrane. Moreover, the tensile strength and thermal decomposition temperature of the PVA/Gol/TpHz membrane were increased from 130.31 MPa to 120.90 °C to 442.05 MPa and 246.8 °C, respectively. The membrane structure and separation performances remained stable during the 80-h pervaporation test, which suggests potential for industrial applications.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123515"},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720784","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}
Pub Date : 2024-11-17DOI: 10.1016/j.memsci.2024.123516
Xin Tong , Ning Chen , Yushu Sui , Yixuan Liu , Dongru Chen , Qiuyu Miao , Jinhui Pang , Zhonghua Tang , Xiaorui Guo , Ning Cao
Highly permeable polyamide (PA) membranes with precise molecular sieving capabilities are crucial for energy-efficient chemical separations. There is a critical need to design solvent-stabilized membranes with enhanced permeance to improve separation efficiency. In this work, we propose a novel anhydrous interfacial polymerization (IP) method, where flexible polyethyleneimine (PEI) and rigid p-phenylenediamine (PPD) are uniquely dissolved in isopropanol (IPA) and subsequently crosslinked with trimethyl chloride (TMC) in situ to fabricate high-performance PA membranes. Notably, the use of IPA as a solvent represents a significant advancement in membrane fabrication. This approach resulted in PA membranes with a relatively loose selective layer compared to traditional PA membranes, allowing for exceptionally high solvent permeance while maintaining strong rejection performance in organic solvent nanofiltration (OSN). The obtained PEI + PPD/TMC PA membranes demonstrated outstanding ethanol (EtOH) permeance of 46.44 L m−2 h−1 bar−1 in the organic solvent system, along with good rejection for small organic molecules, such as 93.84% for Eriochrome Black T (EBT, 461.38 Da). In addition, the performance of the PEI + PPD/TMC PA membranes remained at a high level even during 510 min of continuous cross-flow filtration, under high pressure (5 bar) testing, and after 6 cycles of separation, which demonstrated their good stability in long-term service. This work establishes a robust foundation for employing anhydrous IP reactions and innovative solvent systems, such as IPA, to develop high-permeance PA membranes.
具有精确分子筛分能力的高渗透性聚酰胺（PA）膜对于高能效化学分离至关重要。目前亟需设计出具有更强渗透性的溶剂稳定膜，以提高分离效率。在这项工作中，我们提出了一种新型的无水界面聚合（IP）方法，即将柔性聚乙烯亚胺（PEI）和刚性对苯二胺（PPD）独特地溶解在异丙醇（IPA）中，然后在原位与三甲基氯化物（TMC）交联，以制造高性能 PA 膜。值得注意的是，使用异丙醇作为溶剂代表了膜制造技术的一大进步。与传统的 PA 膜相比，这种方法制造出的 PA 膜具有相对疏松的选择性层，在保持有机溶剂纳滤（OSN）的强排斥性能的同时，还具有极高的溶剂渗透性。所获得的 PEI + PPD/TMC PA 膜在有机溶剂系统中的乙醇（EtOH）渗透率高达 46.44 L m-2 h-1 bar-1，对小分子有机物也有很好的抑制作用，如对 Eriochrome Black T（EBT，461.38 Da）的抑制率为 93.84%。此外，PEI + PPD/TMC PA 膜的性能在 510 分钟的连续交叉流过滤、高压（5 巴）测试和 6 个分离周期后仍保持在较高水平，这表明它们在长期使用中具有良好的稳定性。这项工作为利用无水 IP 反应和创新溶剂系统（如 IPA）开发高渗透 PA 膜奠定了坚实的基础。
{"title":"Anhydrous interfacial polymerization induced by isopropanol to construct high permeance polyamide membranes for organic solvent nanofiltration","authors":"Xin Tong , Ning Chen , Yushu Sui , Yixuan Liu , Dongru Chen , Qiuyu Miao , Jinhui Pang , Zhonghua Tang , Xiaorui Guo , Ning Cao","doi":"10.1016/j.memsci.2024.123516","DOIUrl":"10.1016/j.memsci.2024.123516","url":null,"abstract":"<div><div>Highly permeable polyamide (PA) membranes with precise molecular sieving capabilities are crucial for energy-efficient chemical separations. There is a critical need to design solvent-stabilized membranes with enhanced permeance to improve separation efficiency. In this work, we propose a novel anhydrous interfacial polymerization (IP) method, where flexible polyethyleneimine (PEI) and rigid p-phenylenediamine (PPD) are uniquely dissolved in isopropanol (IPA) and subsequently crosslinked with trimethyl chloride (TMC) in situ to fabricate high-performance PA membranes. Notably, the use of IPA as a solvent represents a significant advancement in membrane fabrication. This approach resulted in PA membranes with a relatively loose selective layer compared to traditional PA membranes, allowing for exceptionally high solvent permeance while maintaining strong rejection performance in organic solvent nanofiltration (OSN). The obtained PEI + PPD/TMC PA membranes demonstrated outstanding ethanol (EtOH) permeance of 46.44 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> in the organic solvent system, along with good rejection for small organic molecules, such as 93.84% for Eriochrome Black T (EBT, 461.38 Da). In addition, the performance of the PEI + PPD/TMC PA membranes remained at a high level even during 510 min of continuous cross-flow filtration, under high pressure (5 bar) testing, and after 6 cycles of separation, which demonstrated their good stability in long-term service. This work establishes a robust foundation for employing anhydrous IP reactions and innovative solvent systems, such as IPA, to develop high-permeance PA membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123516"},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720907","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}
The objective of this research was to enhance the H2 permselectivity of Allylhydridopolycarbosilane (AHPCS)-derived membranes through water plasma (WP) modification and subsequent pyrolysis. The WP modification, applied for 10 s, significantly improved the surface properties of the membranes to form ≡ Si–H, leading to enhanced H2 permselectivity. Pyrolysis at 500−700 °C further transformed the membranes into a dense ceramic structure while maintaining high permeability for He and H2 (0.3–1 × 10−6 mol/(m2 s Pa)), achieved a significant increase in the permeance ratios of conventional SiC membrane from approximately 20 to 300 for H2/N2 and from 80 to 500 for He/N2. Structural evolution analyses via Water contact angle (WCA) and X-Ray photoelectron spectroscopy (XPS) confirmed significant surface oxidation of ≡ Si–H groups to silanol ones via WP and condensation via pyrolysis. These modifications resulted in a structure ≡ of Si–O–Si ≡ on the surface, but SiC in bulk had markedly higher selectivity and permeance than AHPCS membranes pristine and modified with other methods. This design offers excellent thermal and chemical resistance, particularly for small to mid-sized molecules like He and H2.
本研究的目的是通过水等离子体（WP）改性和随后的热解来提高烯丙基hydridopolycarbosilane（AHPCS）衍生膜的H2过选择性。经过 10 秒钟的水等离子体改性，膜的表面性质得到了显著改善，形成了≡Si-H，从而提高了对 H2 的选择性。500-700 °C 高温分解进一步将膜转化为致密的陶瓷结构，同时保持了对 He 和 H2 的高渗透率（0.3-1 × 10-6 mol/(m2 s Pa)），实现了传统 SiC 膜渗透率的显著提高，对 H2/N2 的渗透率从约 20 提高到 300，对 He/N2 的渗透率从 80 提高到 500。通过水接触角（WCA）和 X 射线光电子能谱（XPS）进行的结构演化分析证实，≡Si-H 基团通过可湿性粉末氧化成硅醇基团，并通过热分解缩聚成硅烷醇基团。这些改性导致表面形成了≡Si-O-Si ≡结构，但与原始的 AHPCS 膜和用其他方法改性的 AHPCS 膜相比，块状 SiC 的选择性和渗透性明显更高。这种设计具有出色的耐热性和耐化学性，特别是对 He 和 H2 等中小分子而言。
{"title":"Surface oxidation via water plasma for increased H2 permselectivity of Allylhydridopolycarbosilane (AHPCS)-derived SiC membranes","authors":"Gusni Sushanti , Shun Aoyama , Norihiro Moriyama , Hiroki Nagasawa , Masakoto Kanezashi , Toshinori Tsuru","doi":"10.1016/j.memsci.2024.123521","DOIUrl":"10.1016/j.memsci.2024.123521","url":null,"abstract":"<div><div>The objective of this research was to enhance the H<sub>2</sub> permselectivity of Allylhydridopolycarbosilane (AHPCS)-derived membranes through water plasma (WP) modification and subsequent pyrolysis. The WP modification, applied for 10 s, significantly improved the surface properties of the membranes to form ≡ Si–H, leading to enhanced H<sub>2</sub> permselectivity. Pyrolysis at 500−700 °C further transformed the membranes into a dense ceramic structure while maintaining high permeability for He and H<sub>2</sub> (0.3–1 × 10<sup>−6</sup> mol/(m<sup>2</sup> s Pa)), achieved a significant increase in the permeance ratios of conventional SiC membrane from approximately 20 to 300 for H<sub>2</sub>/N<sub>2</sub> and from 80 to 500 for He/N<sub>2</sub>. Structural evolution analyses via Water contact angle (WCA) and X-Ray photoelectron spectroscopy (XPS) confirmed significant surface oxidation of ≡ Si–H groups to silanol ones via WP and condensation via pyrolysis. These modifications resulted in a structure ≡ of Si–O–Si ≡ on the surface, but SiC in bulk had markedly higher selectivity and permeance than AHPCS membranes pristine and modified with other methods. This design offers excellent thermal and chemical resistance, particularly for small to mid-sized molecules like He and H<sub>2</sub>.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123521"},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720459","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}
Pub Date : 2024-11-16DOI: 10.1016/j.memsci.2024.123513
Idit Shefer, Liat Birnhack, Razi Epsztein
To improve the solute-specific selectivity of nanofiltration (NF) membranes, a fundamental understanding of the transport mechanisms in these membranes is required. In this study, we explored the selectivity trends of common anionic pollutants (i.e., nitrate and perchlorate) compared to the common chloride anion and examined the underlying transport mechanisms for these trends in loose polyamide NF membranes. Permeation experiments show that nitrate and perchlorate, despite being polyatomic and larger, permeate the membrane faster than the monoatomic, spherical chloride, suggesting that other mechanisms beyond size and charge exclusion govern the separation. Significantly higher enthalpic barriers measured for the transport of chloride compared to nitrate and perchlorate elucidated the important role of ion dehydration in the selectivity observed. To further support the influence of dehydration, we systematically altered the ions’ hydration by introducing various organic aliphatic alcohols of different hydrophobicity into the feed solution. The inclusion of aliphatic alcohols intensified the chaotropic characteristics of nitrate and perchlorate, augmenting their capacity to dehydrate, as reflected by their enhanced permeation and reduced enthalpic barrier in the presence of alcohols. We also demonstrated that this effect is boosted when a strong kosmotropic anion like sulfate is added to the system due to its counter effect on water structuring. We conclude with proposing mechanisms for the anion behavior in water-alcohol solutions that highlight the critical importance of ionic hydration in transmembrane permeation.
{"title":"The importance of ionic hydration in the transport of monovalent anions through nanofiltration membranes","authors":"Idit Shefer, Liat Birnhack, Razi Epsztein","doi":"10.1016/j.memsci.2024.123513","DOIUrl":"10.1016/j.memsci.2024.123513","url":null,"abstract":"<div><div>To improve the solute-specific selectivity of nanofiltration (NF) membranes, a fundamental understanding of the transport mechanisms in these membranes is required. In this study, we explored the selectivity trends of common anionic pollutants (i.e., nitrate and perchlorate) compared to the common chloride anion and examined the underlying transport mechanisms for these trends in loose polyamide NF membranes. Permeation experiments show that nitrate and perchlorate, despite being polyatomic and larger, permeate the membrane faster than the monoatomic, spherical chloride, suggesting that other mechanisms beyond size and charge exclusion govern the separation. Significantly higher enthalpic barriers measured for the transport of chloride compared to nitrate and perchlorate elucidated the important role of ion dehydration in the selectivity observed. To further support the influence of dehydration, we systematically altered the ions’ hydration by introducing various organic aliphatic alcohols of different hydrophobicity into the feed solution. The inclusion of aliphatic alcohols intensified the chaotropic characteristics of nitrate and perchlorate, augmenting their capacity to dehydrate, as reflected by their enhanced permeation and reduced enthalpic barrier in the presence of alcohols. We also demonstrated that this effect is boosted when a strong kosmotropic anion like sulfate is added to the system due to its counter effect on water structuring. We conclude with proposing mechanisms for the anion behavior in water-alcohol solutions that highlight the critical importance of ionic hydration in transmembrane permeation.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123513"},"PeriodicalIF":8.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720785","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}
Pub Date : 2024-11-16DOI: 10.1016/j.memsci.2024.123503
Guangyao Fan , Dongyang Li , Jing Wang , Meixia Shan , Guanying Dong , Xiaoquan Feng , Yatao Zhang
ZIF-8-based Mixed-Matrix Membranes (MMMs) have demonstrated promising potential for propylene/propane separation, but improvements in gas separation efficiency are hindered by the interfacial compatibility between ZIF-8 and the polymer matrix. In this study, we employed molecular modeling and simulations to construct and quantitatively compare the microstructural and energetic properties of three MMMs, including ZIF-8 with PIM-1, 6FDA-durene, and PIM-6FDA-OH. We assessed the applicability of the General Amber Force Field for modeling these MMMs and confirmed its validity. A protocol was developed to accurately define the interface region of the MMMs, ensuring reliability in calculating interfacial properties. Using this defined interface, we evaluated and compared the atomic concentration profile, interfacial length, polymer porosity, pore size distribution, and interfacial binding energy. Our findings indicate an order of interfacial compatibility as follows: ZIF-8/PIM-6FDA-OH > ZIF-8/6FDA-durene > ZIF-8/PIM-1, aligning well with literature reports. Further molecular-level analysis through radial distribution functions and dihedral angle distributions supported this compatibility order. Additionally, we explored the impact of modeling size on characterizing interfacial properties, affirming that our model effectively balances simulation accuracy and efficiency. Propylene/propane adsorption properties were also computed, revealing potential mechanisms for enhanced gas solubility in different MMMs. Most importantly, this comprehensive investigation led to the development and validation of an interface screening system, providing a reliable and efficient method for designing or screening polymer-filler pairs to improve gas separation performance.
{"title":"Toward quantitative evaluations of interfacial compatibility of ZIF-8 based mixed-matrix membranes via molecular simulations","authors":"Guangyao Fan , Dongyang Li , Jing Wang , Meixia Shan , Guanying Dong , Xiaoquan Feng , Yatao Zhang","doi":"10.1016/j.memsci.2024.123503","DOIUrl":"10.1016/j.memsci.2024.123503","url":null,"abstract":"<div><div>ZIF-8-based Mixed-Matrix Membranes (MMMs) have demonstrated promising potential for propylene/propane separation, but improvements in gas separation efficiency are hindered by the interfacial compatibility between ZIF-8 and the polymer matrix. In this study, we employed molecular modeling and simulations to construct and quantitatively compare the microstructural and energetic properties of three MMMs, including ZIF-8 with PIM-1, 6FDA-durene, and PIM-6FDA-OH. We assessed the applicability of the General Amber Force Field for modeling these MMMs and confirmed its validity. A protocol was developed to accurately define the interface region of the MMMs, ensuring reliability in calculating interfacial properties. Using this defined interface, we evaluated and compared the atomic concentration profile, interfacial length, polymer porosity, pore size distribution, and interfacial binding energy. Our findings indicate an order of interfacial compatibility as follows: ZIF-8/PIM-6FDA-OH > ZIF-8/6FDA-durene > ZIF-8/PIM-1, aligning well with literature reports. Further molecular-level analysis through radial distribution functions and dihedral angle distributions supported this compatibility order. Additionally, we explored the impact of modeling size on characterizing interfacial properties, affirming that our model effectively balances simulation accuracy and efficiency. Propylene/propane adsorption properties were also computed, revealing potential mechanisms for enhanced gas solubility in different MMMs. Most importantly, this comprehensive investigation led to the development and validation of an interface screening system, providing a reliable and efficient method for designing or screening polymer-filler pairs to improve gas separation performance.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"716 ","pages":"Article 123503"},"PeriodicalIF":8.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720781","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}
Pub Date : 2024-11-16DOI: 10.1016/j.memsci.2024.123512
Zhi-Peng Wang, Ziyang Cheng, Qiaohong Liu, Chunguang Hou, Quan-Fu An
Blending hydrophilic additives is an effective method to improve the surface hydrophilcility and antifouling property of ultrafiltration membranes. In this study, we prepared a series of polysulfate (PSE) hollow fiber membranes (HFMs) containing a zwitterion-based copolymer, poly(4-vinylpyridine-co-methylacryloxyethyl phosphocholine), with varying monomer ratios and blending quantities. The relationship between cast solution properties and phase separation behavior was investigated, as well as the impacts of copolymer composition and amount on the separation performances and antifouling abilities of the membranes. A higher hydrophilic monomer ratio and more copolymer addition of zwitterionic copolymer would facilitate surface segregation, increasing the hydrophilicity of membrane surface and generating a dense hydration layer. This layer can resist macromolecule contaminants and promote water molecular transport. Furthermore, a more compacted skin layer improves separation ability. The optimized PSE HFMs had water fluxes around 140 L m−2 h−1, BSA rejections over 97 %, and flux recovery rates over 92 % during operation. Moreover, the membrane demonstrated ultra-low flux-sacrifice when applied to protein solutions while maintaining a high rejection rate, which indicates the distinctive and strong competitiveness of PSE/P(4VP-co-MPC) HFMs.
混合亲水添加剂是提高超滤膜表面亲水性和防污性能的有效方法。在本研究中，我们制备了一系列聚硫酸盐（PSE）中空纤维膜（HFMs），其中含有一种基于齐聚物的共聚物--聚（4-乙烯基吡啶-共甲基丙烯酰氧乙基磷酰胆碱），单体比例和混合量各不相同。研究了浇注溶液特性与相分离行为之间的关系，以及共聚物成分和用量对膜的分离性能和防污能力的影响。亲水性单体比例越高，共聚物中添加的共聚物越多，就越有利于表面分离，从而增加膜表面的亲水性，形成致密的水合层。该层可抵御大分子污染物，促进水分子的传输。此外，更紧密的表皮层还能提高分离能力。经过优化的 PSE HFM 在运行期间的水通量约为 140 L m-2 h-1，BSA 排斥率超过 97%，通量回收率超过 92%。此外，该膜在应用于蛋白质溶液时表现出超低的通量-孔隙率，同时保持较高的剔除率，这表明 PSE/P(4VP-co-MPC)高频膜具有独特而强大的竞争力。
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Pub Date : 2024-11-15DOI: 10.1016/j.memsci.2024.123502
Yurong Yin , Can Li , Daniel Yee Fan Ng , Rong Wang
The development of acid-resistant nanofiltration (NF) membranes has drawn much attention due to their application in industrial wastewater treatment. In this work, we utilized polyethyleneimine (PEI) and cyanuric chloride (CC) to conduct the first interfacial polymerization (IP) reaction on the polyethersulfone (PES) hollow fiber substrate, followed by the secondary IP process using tris(2-aminoethyl) amine (TAEA) to react with the residual chloride groups after the first IP to improve the positive charge intensity of the membrane surface. Compared to the pristine membrane formed after the first IP, the TAEA-optimized membrane exhibited a high pure water permeability (PWP) of 25.2 L m−2 h−1 bar−1 and nearly 90 % rejection to MgCl2 at 2 bar operating pressure. Meanwhile, when treating synthetic electroplating rinse water, the membrane was still able to achieve 85 % rejections to Cu2+ and Ni2+ ions during a 7-day operation test under pH of 1 condition. The results demonstrate the good potential of the membrane for heavy metal ions removal in industrial acidic wastewater.
由于在工业废水处理中的应用，耐酸纳滤膜的开发备受关注。在这项工作中，我们利用聚乙烯亚胺（PEI）和氯化氰（CC）在聚醚砜（PES）中空纤维基材上进行了第一次界面聚合（IP）反应，然后利用三（2-氨基乙基）胺（TAEA）进行了二次 IP 处理，与第一次 IP 后残留的氯基发生反应，以提高膜表面的正电荷强度。与第一次 IP 后形成的原始膜相比，TAEA 优化膜的纯水渗透率（PWP）高达 25.2 L m-2 h-1 bar-1，在 2 bar 工作压力下对氯化镁的排斥率接近 90%。同时，在处理合成电镀冲洗水时，该膜在 pH 值为 1 的条件下进行了为期 7 天的运行测试，对 Cu2+ 和 Ni2+ 离子的截留率仍能达到 85%。这些结果证明了该膜在工业酸性废水中去除重金属离子的良好潜力。
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Pub Date : 2024-11-15DOI: 10.1016/j.memsci.2024.123492
Zhiyun Kong , Bing Zhang , Xiaolei Wang , Zifei Qi , Chan Huang , Haike Li , Huan Zhang , Huicai Wang
To address the permeability-selectivity trade-off of organic solvent nanofiltration (OSN) membranes, a gel composite membrane was fabricated by the complexation of tannic acid (TA) and ferric ions (Fe3+) on the surface of self-supported calcium alginate (CaAlg) gel membrane. The three-dimensional network of the CaAlg substrate serves as a channel for rapid solvent transport, while the dense TA/Fe3+ metal-phenol network achieves solute rejection. The chemical structure, morphology, pore size, zeta potential and mechanical properties of the CaAlg substrate and the gel composite membrane were characterized. Dye/solvent separation and solvent resistance were investigated. The results indicate that the TA/Fe3+ separation layer reduces the pore size, increases the negative charge and improves the mechanical properties of the gel membrane. By optimizing the TA/Fe3+ complexation conditions, the gel composite membrane has an ethanol permeance of 19.5 L m−2 h−1 bar−1 and a congo red (CR) rejection of 99.0 %, and the separation performance is almost unchanged during 60 d of immersion in N, N-dimethlformamide (DMF). In addition, the composite membrane could separate CR from DMF and acetone, as well as cationic and anionic dyes in ethanol. This work provides a simple and environmentally friendly method to prepare an OSN membrane with high solvent permeance and harsh solvent stability, which is promising for solvent purification and recovery.
为了解决有机溶剂纳滤膜（OSN）的渗透性-选择性权衡问题，研究人员通过在自支撑海藻酸钙（CaAlg）凝胶膜表面络合单宁酸（TA）和铁离子（Fe3+），制备了一种凝胶复合膜。CaAlg 基质的三维网络可作为快速传输溶剂的通道，而致密的 TA/Fe3+ 金属酚网络可实现溶质排斥。研究人员对 CaAlg 基质和凝胶复合膜的化学结构、形态、孔径、Zeta 电位和机械性能进行了表征。对染料/溶剂分离和耐溶剂性进行了研究。结果表明，TA/Fe3+ 分离层缩小了孔径，增加了负电荷，并改善了凝胶膜的机械性能。通过优化 TA/Fe3+ 复合条件，凝胶复合膜的乙醇渗透率达到 19.5 L m-2 h-1 bar-1，刚果红（CR）剔除率达到 99.0%，并且在 N，N-二甲基甲酰胺（DMF）中浸泡 60 d 后分离性能几乎保持不变。此外，复合膜还能分离 DMF 和丙酮中的刚果红，以及乙醇中的阳离子和阴离子染料。这项工作提供了一种简单而环保的方法来制备具有高溶剂渗透性和苛刻溶剂稳定性的 OSN 膜，有望用于溶剂净化和回收。
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