Journal of Membrane Science最新文献_第7页

Sustainable ammonia recovery in electrochemical membranes: The critical role of electromigration

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-27 DOI: 10.1016/j.memsci.2025.124018

Siyao Qi , Wen Zhang , Guy Z. Ramon , Avner Ronen

Ammonia (NH₃) is a vital chemical widely used in fertilizers, industry, and as a potential energy carrier. However, conventional ammonia production via the Haber-Bosch process is highly energy-intensive, consuming approximately 13.9 kWh per kg of nitrogen. Additionally, nitrogen-rich wastewater contributes to eutrophication and aquatic toxicity, necessitating sustainable recovery solutions. This study introduces an electrochemical membrane stripping (EMS) system incorporating hydrophobic, electrically conducting membranes (ECMs) to enhance ammonia recovery. By applying a controlled electric field and optimizing cathodic potential and crossflow velocity, the system efficiently transports ammonium (NH₄⁺) toward the cathodic membrane, where a localized pH shift converts it into free ammonia (NH₃), eliminating the need for chemical pH adjustment.

Under optimal conditions, the EMS system achieved 88 % ammonia recovery with a high flux of 37 ± 1.45 g m⁻² d⁻¹, representing a 33.5 % improvement over conventional methods. Mass balance analysis confirmed electromigration as a key transport mechanism, leading to a threefold increase in ammonia concentration at the membrane surface. Additionally, the system demonstrated high energy efficiency, with a specific energy consumption of 2 ± 0.15 kWh per kg of nitrogen, making it a cost-effective alternative for liquid fertilizer production.

As a proof-of-concept, the EMS system was successfully tested on real municipal wastewater, highlighting its practical viability. However, further research is needed to assess long-term stability, scalability, and integration with wastewater treatment infrastructure. This study demonstrates EMS as a promising technology for sustainable nitrogen recovery, supporting circular economy initiatives.

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引用次数: 0

Enhancing reverse osmosis membrane performance via interfacial diffusion control using porous graphene oxide

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-27 DOI: 10.1016/j.memsci.2025.124040

Young Jae Kim , Byung Kwan Lee , Inho Park , Chaewon Youn , Myung-Seok Lee , Jung-Hyun Lee , Ho Bum Park

The development of polyamide (PA) thin-film composite (TFC) membranes with enhanced water permeance and salt rejection is essential for energy-efficient desalination. This study introduces a reverse osmosis (RO) membrane that achieves rapid water transport and high salt rejection through precise control of interfacial polymerization (IP), enabled by porous graphene oxide (PGO) with optimally sized nanopores. These nanopores act as diffusion pathways for m-phenylenediamine (MPD) during IP in a confined space, reducing residual unreacted MPD and creating additional water transport channels. This process facilitates the formation of a highly crosslinked and permeable PA selective layer. The thin-film nanocomposite (TFN) membrane incorporating PGO etched for 3 h exhibited outstanding water permeance of 3.57 L m⁻² h⁻¹ bar⁻¹ and NaCl rejection of 98.7 %, surpassing state-of-the-art GO-modified RO membranes. Additionally, the membrane demonstrated superior antifouling performance and long-term operational stability. Structural and performance comparisons with TFN membranes incorporating PGO with varying nanopore sizes, controlled via etching time, elucidated the transport mechanism across the membrane. This work highlights a robust strategy for manufacturing high-performance TFC membranes by modulating interfacial diffusion during IP.

{"title":"Enhancing reverse osmosis membrane performance via interfacial diffusion control using porous graphene oxide","authors":"Young Jae Kim , Byung Kwan Lee , Inho Park , Chaewon Youn , Myung-Seok Lee , Jung-Hyun Lee , Ho Bum Park","doi":"10.1016/j.memsci.2025.124040","DOIUrl":"10.1016/j.memsci.2025.124040","url":null,"abstract":"<div><div>The development of polyamide (PA) thin-film composite (TFC) membranes with enhanced water permeance and salt rejection is essential for energy-efficient desalination. This study introduces a reverse osmosis (RO) membrane that achieves rapid water transport and high salt rejection through precise control of interfacial polymerization (IP), enabled by porous graphene oxide (PGO) with optimally sized nanopores. These nanopores act as diffusion pathways for <em>m</em>-phenylenediamine (MPD) during IP in a confined space, reducing residual unreacted MPD and creating additional water transport channels. This process facilitates the formation of a highly crosslinked and permeable PA selective layer. The thin-film nanocomposite (TFN) membrane incorporating PGO etched for 3 h exhibited outstanding water permeance of 3.57 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> and NaCl rejection of 98.7 %, surpassing state-of-the-art GO-modified RO membranes. Additionally, the membrane demonstrated superior antifouling performance and long-term operational stability. Structural and performance comparisons with TFN membranes incorporating PGO with varying nanopore sizes, controlled via etching time, elucidated the transport mechanism across the membrane. This work highlights a robust strategy for manufacturing high-performance TFC membranes by modulating interfacial diffusion during IP.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 124040"},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

New insights on the organic fouling mechanism of ultrafiltration membranes using hybrid QCM-D–LSPR

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-26 DOI: 10.1016/j.memsci.2025.124044

Diaa AbuKhadra, Yoram Oren, Moshe Herzberg

Organic fouling of ultrafiltration (UF) membranes is a major drawback and therefore, a rigorous analysis of the interactions of macromolecules with the outer membrane surface as well as with the confined porous membrane structure is required. This work provides new insights into the interplay between the interactions and conformation of alginate, a model organic foulant, as it penetrates the porous structure of an UF membrane. Alginate, like other organic foulants, can adopt conformations and orientations on the membrane surface that change in response to the aqueous conditions. In this work, adsorbed alginate layers were tested on a membrane-mimetic sensor surface using a hybrid system consisting of localized surface plasmon resonance (LSPR) sensing and quartz crystal microbalance with dissipation monitoring (QCM-D). The alginate conformation and adhesion on the sensor were consistent with the effects of alginate penetrating to the UF membrane pores affecting permeability at various ionic strengths. To study the interactions and conformational changes of alginate on the surface, the membrane surface and the hybrid sensor were given a positive charge by modifying them with species bearing primary amine groups, 2-aminoethyl methacrylate and 3-aminopropyl triethoxysilane, respectively. Intriguingly, on the pristine surfaces, increasing ionic strength induced a reversible increase in alginate areal density as measured by LSPR, indicating changes in alginate conformation, which increased the effective UF membrane pore diameter and increased membrane permeability. In contrast, the modified membranes with positive surfaces did not exhibit these changes in alginate conformation caused by ionic strength and membrane permeability showed no response to the aqueous ionic strength. This novel analysis of foulant conformation on a membrane-mimetic LSPR sensor, was further confirmed by the standard pore blocking model. QCM-D analysis revealed the expected responses to surface charge and ionic strength, i.e., the alginate layer's viscoelasticity increased on the positively charged surface and with increasing ionic strength. These analyses at the nanometer scale provide critical mechanistic insight into the way fouling reduces UF membrane performance.

{"title":"New insights on the organic fouling mechanism of ultrafiltration membranes using hybrid QCM-D–LSPR","authors":"Diaa AbuKhadra, Yoram Oren, Moshe Herzberg","doi":"10.1016/j.memsci.2025.124044","DOIUrl":"10.1016/j.memsci.2025.124044","url":null,"abstract":"<div><div>Organic fouling of ultrafiltration (UF) membranes is a major drawback and therefore, a rigorous analysis of the interactions of macromolecules with the outer membrane surface as well as with the confined porous membrane structure is required. This work provides new insights into the interplay between the interactions and conformation of alginate, a model organic foulant, as it penetrates the porous structure of an UF membrane. Alginate, like other organic foulants, can adopt conformations and orientations on the membrane surface that change in response to the aqueous conditions. In this work, adsorbed alginate layers were tested on a membrane-mimetic sensor surface using a hybrid system consisting of localized surface plasmon resonance (LSPR) sensing and quartz crystal microbalance with dissipation monitoring (QCM-D). The alginate conformation and adhesion on the sensor were consistent with the effects of alginate penetrating to the UF membrane pores affecting permeability at various ionic strengths. To study the interactions and conformational changes of alginate on the surface, the membrane surface and the hybrid sensor were given a positive charge by modifying them with species bearing primary amine groups, 2-aminoethyl methacrylate and 3-aminopropyl triethoxysilane, respectively. Intriguingly, on the pristine surfaces, increasing ionic strength induced a reversible increase in alginate areal density as measured by LSPR, indicating changes in alginate conformation, which increased the effective UF membrane pore diameter and increased membrane permeability. In contrast, the modified membranes with positive surfaces did not exhibit these changes in alginate conformation caused by ionic strength and membrane permeability showed no response to the aqueous ionic strength. This novel analysis of foulant conformation on a membrane-mimetic LSPR sensor, was further confirmed by the standard pore blocking model. QCM-D analysis revealed the expected responses to surface charge and ionic strength, i.e., the alginate layer's viscoelasticity increased on the positively charged surface and with increasing ionic strength. These analyses at the nanometer scale provide critical mechanistic insight into the way fouling reduces UF membrane performance.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"725 ","pages":"Article 124044"},"PeriodicalIF":8.4,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143725754","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Co-assembly of perfluorinated sulfonic-acid ionomer and tetraphenylporphyrin tetrasulfonic-acid contributes to high-performance proton-exchange membranes

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-26 DOI: 10.1016/j.memsci.2025.124041

Wenshuo Wang , Pengju Pan , Yongzhong Bao

To meet improved requirements for proton-exchange membranes (PEMs) applied in medium- and low-temperature fuel cells, novel PEMs with superior performance are prepared by using commercial perfluorinated sulfonic-acid ionomer (PFSA) and a dopant, tetraphenylporphyrin tetrasulfonic-acid (TPPS). Different from physically blending PFSA with another polymer or a nano-material, the membrane-forming mechanism of TPPS modified PFSA PEMs is highly dependent on the efficient interaction between PFSA and TPPS molecules. The unique three-part nested hydrophilic-hydrophobic-hydrophilic molecular structure of TPPS plays a crucial role in the co-assembly of PFSA with TPPS. The more intensive ionic cross-linking and hydrogen-bond networks are formed through hydrophilic groups in the outer and internal parts of TPPS and sulfonic-acid groups of PFSA. Meanwhile, secondary cross-linking of these hydrophilic groups is induced by rigid hydrophobic groups in the middle part of TPPS. Therefore, these molecular interactions induce the formation of more stable and stronger nano-phase separation with more uniform size. This novel nano-phase separation structure endows PEMs with elevated applicable temperatures, much increased proton conductivity and thus superior fuel cell performances, which are the keys to the development of more advanced hydrogen fuel cells.

{"title":"Co-assembly of perfluorinated sulfonic-acid ionomer and tetraphenylporphyrin tetrasulfonic-acid contributes to high-performance proton-exchange membranes","authors":"Wenshuo Wang , Pengju Pan , Yongzhong Bao","doi":"10.1016/j.memsci.2025.124041","DOIUrl":"10.1016/j.memsci.2025.124041","url":null,"abstract":"<div><div>To meet improved requirements for proton-exchange membranes (PEMs) applied in medium- and low-temperature fuel cells, novel PEMs with superior performance are prepared by using commercial perfluorinated sulfonic-acid ionomer (PFSA) and a dopant, tetraphenylporphyrin tetrasulfonic-acid (TPPS). Different from physically blending PFSA with another polymer or a nano-material, the membrane-forming mechanism of TPPS modified PFSA PEMs is highly dependent on the efficient interaction between PFSA and TPPS molecules. The unique three-part nested hydrophilic-hydrophobic-hydrophilic molecular structure of TPPS plays a crucial role in the co-assembly of PFSA with TPPS. The more intensive ionic cross-linking and hydrogen-bond networks are formed through hydrophilic groups in the outer and internal parts of TPPS and sulfonic-acid groups of PFSA. Meanwhile, secondary cross-linking of these hydrophilic groups is induced by rigid hydrophobic groups in the middle part of TPPS. Therefore, these molecular interactions induce the formation of more stable and stronger nano-phase separation with more uniform size. This novel nano-phase separation structure endows PEMs with elevated applicable temperatures, much increased proton conductivity and thus superior fuel cell performances, which are the keys to the development of more advanced hydrogen fuel cells.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"725 ","pages":"Article 124041"},"PeriodicalIF":8.4,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thin-film composite membrane improved by modified structure rearrangement process (mSRP) for rapidly aqueous and solvents separation

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-26 DOI: 10.1016/j.memsci.2025.124047

Bai-He Chen , Hao-Ze Deng , Rui Han , Man Zhu , Rui-Wen Pan , Xue-Wei Zhang , Zhen-Liang Xu , Hong-Bo Li , Sun-Jie Xu

This study aims to develop an advanced organic solvent nanofiltration (OSN) membrane by incorporating an adamantane-amide active layer through a modified structure rearrangement process (mSRP) combined with host-guest interactions. The membrane was fabricated by treating a commercial reverse osmosis (RO) membrane with solutions containing polysaccharides and adamantane monomers, obtaining significantly enhanced separation performance. The modified membrane exhibited a “mesh-like” morphology and increased surface roughness which contributed to substantially higher permeability and retention rates compared to those of pristine RO membrane. Specifically, the optimal membrane attained a permeability of 9.3 L m⁻² h⁻¹·bar⁻¹, representing an increase by 111.4 % relative to the pristine membrane, while maintaining a rejection rate of 94.0 % for the commonly used erythromycin antibiotic. The rearrangement behavior and mechanism of the host-guest interactions were investigated using density functional calculations. Long-term operational tests confirmed the stability of the membrane and its potential for industrial applications. This study introduced a novel approach for upgrading commercial RO membranes for efficient OSN applications, thereby contributing to the development of sustainable separation technologies in the biomedical sector.

本研究旨在开发一种先进的有机溶剂纳滤膜（OSN），通过改性结构重排过程（mSRP）结合主客体相互作用，将金刚烷-酰胺活性层纳入其中。这种膜是用含有多糖和金刚烷单体的溶液处理商用反渗透膜后制成的，分离性能显著提高。改性膜呈现出 "网状 "形态，表面粗糙度增加，与原始反渗透膜相比，渗透率和截留率大幅提高。具体来说，最佳膜的渗透率达到了 9.3 L m-2 h-1-bar-1 ，与原始膜相比提高了 111.4%，同时对常用红霉素抗生素的截留率保持在 94.0%。利用密度泛函计算研究了主客体相互作用的重排行为和机制。长期运行测试证实了该膜的稳定性及其工业应用潜力。这项研究引入了一种新方法，用于升级商业反渗透膜，使其高效地应用于有机碳网，从而为生物医学领域可持续分离技术的发展做出了贡献。

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引用次数: 0

Facile fabrication of SiO2-ZrO2/Al2O3 ceramic hollow fiber nanofiltration membrane for hot industrial wastewater treatment

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-26 DOI: 10.1016/j.memsci.2025.123983

Beibei Liu , Zhigang Wang , Xiaoyao Tan

Ceramic nanofiltration (NF) membranes exhibit superior stability and can operate effectively under harsh conditions. However, the tedious fabrication processes always result in a high cost for ceramic NF membranes. In this work, SiO₂–ZrO₂/Al₂O₃ ceramic hollow fiber NF membranes are facilely fabricated. Boehmite sol only is used to create the interlayer between the support and the SiO₂–ZrO₂ separation layer. By optimizing the pore size and thickness of this interlayer, the modification process for the support is streamlined from multiple steps to a single step. Additionally, the required number of SiO₂–ZrO₂ layer coatings is substantially reduced, significantly enhancing process efficiency. Meanwhile, this work also identifies the characteristics of an appropriate interlayer that meets the requirements for effectively coating the SiO₂–ZrO₂ layer. Finally, an optimized ceramic NF membrane with a molecular weight cut-off (MWCO) of 1000 Da and an average pore size of 1.59 nm is achieved. This ceramic NF membrane reveals superior retention for most dyes and high transport for monovalent salts (retention <20 %). In the application of dye desalination for hot textile wastewater treatment, the membrane displays an excellent permeance of more than 6 LMH/bar and good selectivity for dye/salt mixture solutions at 60 °C (e.g. the separation factors for EB/NaCl, BS/NaCl, CR/NaCl, and EBT/NaCl attained 256, 872, 100 and 433, respectively). Meanwhile, the membrane exhibits outstanding hydrothermal stability and remarkable resistance to membrane fouling under harsh acid and alkali conditions, maintaining stable separation performance for dye desalination over 100 h at 60 °C.

{"title":"Facile fabrication of SiO2-ZrO2/Al2O3 ceramic hollow fiber nanofiltration membrane for hot industrial wastewater treatment","authors":"Beibei Liu , Zhigang Wang , Xiaoyao Tan","doi":"10.1016/j.memsci.2025.123983","DOIUrl":"10.1016/j.memsci.2025.123983","url":null,"abstract":"<div><div>Ceramic nanofiltration (NF) membranes exhibit superior stability and can operate effectively under harsh conditions. However, the tedious fabrication processes always result in a high cost for ceramic NF membranes. In this work, SiO<sub>2</sub>–ZrO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ceramic hollow fiber NF membranes are facilely fabricated. Boehmite sol only is used to create the interlayer between the support and the SiO<sub>2</sub>–ZrO<sub>2</sub> separation layer. By optimizing the pore size and thickness of this interlayer, the modification process for the support is streamlined from multiple steps to a single step. Additionally, the required number of SiO<sub>2</sub>–ZrO<sub>2</sub> layer coatings is substantially reduced, significantly enhancing process efficiency. Meanwhile, this work also identifies the characteristics of an appropriate interlayer that meets the requirements for effectively coating the SiO<sub>2</sub>–ZrO<sub>2</sub> layer. Finally, an optimized ceramic NF membrane with a molecular weight cut-off (MWCO) of 1000 Da and an average pore size of 1.59 nm is achieved. This ceramic NF membrane reveals superior retention for most dyes and high transport for monovalent salts (retention <20 %). In the application of dye desalination for hot textile wastewater treatment, the membrane displays an excellent permeance of more than 6 LMH/bar and good selectivity for dye/salt mixture solutions at 60 °C (e.g. the separation factors for EB/NaCl, BS/NaCl, CR/NaCl, and EBT/NaCl attained 256, 872, 100 and 433, respectively). Meanwhile, the membrane exhibits outstanding hydrothermal stability and remarkable resistance to membrane fouling under harsh acid and alkali conditions, maintaining stable separation performance for dye desalination over 100 h at 60 °C.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"726 ","pages":"Article 123983"},"PeriodicalIF":8.4,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Guanidinium covalent organic framework modulated positively charged polyamide membranes toward superior Li+/Mg2+ selectivity

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-26 DOI: 10.1016/j.memsci.2025.124046

Shiyu Zhang , Tianrun Gu , Zhichao Li , Jinqiu Yuan , Chao Yang , Zaichuang Liu , Yu Zheng , Xiangxuan Meng , Xiaolin Yue , Qingyuan Liu , Hui Wang , Runnan Zhang , Zhongyi Jiang

Nanofiltration (NF) membrane separation technology offers significant potential for the effective Li⁺ extraction from salt-lake brines. Attaining high Li⁺/Mg²⁺ selectivity relies on increasing the positively charged density of the NF membrane surface. In this study, a guanidinium covalent organic framework (TbTG) nanosheet is designed to modulate positively charged polyamide (PA) thin-film nanocomposite (TFN) membranes. The TbTG nanosheets are synthesized and deposited on polyethersulfone ( PES) support alongside polyethyleneimine (PEI) to polymerize with trimesoyl chloride (TMC) and generate cross-linked PA-COF networks. The charge density of the membrane surface is increased to +1.48 mC m^-2, nearly twice that of the pristine PA membrane. The enhanced positive chargeability stems from the guanidine and amino groups of the TbTG framework, creating a stronger Donnan exclusion to repel Mg²⁺. Meanwhile, the hydrogen bond interaction between TbTG and PEI monomers brings about decreased pore size of the membranes. Therefore, the optimal PA-COF-3 membrane demonstrates an ultrahigh MgCl₂ rejection of 99.4%, as well as a superior separation factor (

) of 76.5 at a LiCl/MgCl₂ mass ratio of 1:40, which exceeds the performance of most reported NF membranes.

{"title":"Guanidinium covalent organic framework modulated positively charged polyamide membranes toward superior Li+/Mg2+ selectivity","authors":"Shiyu Zhang , Tianrun Gu , Zhichao Li , Jinqiu Yuan , Chao Yang , Zaichuang Liu , Yu Zheng , Xiangxuan Meng , Xiaolin Yue , Qingyuan Liu , Hui Wang , Runnan Zhang , Zhongyi Jiang","doi":"10.1016/j.memsci.2025.124046","DOIUrl":"10.1016/j.memsci.2025.124046","url":null,"abstract":"<div><div>Nanofiltration (NF) membrane separation technology offers significant potential for the effective Li<sup>+</sup> extraction from salt-lake brines. Attaining high Li<sup>+</sup>/Mg<sup>2+</sup> selectivity relies on increasing the positively charged density of the NF membrane surface. In this study, a guanidinium covalent organic framework (TbTG) nanosheet is designed to modulate positively charged polyamide (PA) thin-film nanocomposite (TFN) membranes. The TbTG nanosheets are synthesized and deposited on polyethersulfone ( PES) support alongside polyethyleneimine (PEI) to polymerize with trimesoyl chloride (TMC) and generate cross-linked PA-COF networks. The charge density of the membrane surface is increased to +1.48 mC m<sup>-2</sup>, nearly twice that of the pristine PA membrane. The enhanced positive chargeability stems from the guanidine and amino groups of the TbTG framework, creating a stronger Donnan exclusion to repel Mg<sup>2+</sup>. Meanwhile, the hydrogen bond interaction between TbTG and PEI monomers brings about decreased pore size of the membranes. Therefore, the optimal PA-COF-3 membrane demonstrates an ultrahigh MgCl<sub>2</sub> rejection of 99.4%, as well as a superior separation factor (<span><math></math></span>) of 76.5 at a LiCl/MgCl<sub>2</sub> mass ratio of 1:40, which exceeds the performance of most reported NF membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"725 ","pages":"Article 124046"},"PeriodicalIF":8.4,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tailoring ion networks of block-graft copolymers using click chemistry for high-performance hydrocarbon polymer electrolyte membranes

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-25 DOI: 10.1016/j.memsci.2025.124045

So Youn Lee , Jong-Gil Oh , Dong Hee Kim , Il Seok Chae , Jong Hak Kim

To address the environmental and economic concerns associated with perfluorinated sulfonic acids (PFSAs), we propose a novel approach to synthesize block-graft copolymers for hydrocarbon polymer electrolyte membranes (PEMs) designed for clean energy applications including fuel cells and water electrolysis. This study introduces an efficient “graft-onto” approach using click chemistry, which couples side chains onto a main polymer backbone, enabling the precise structural construction of block-graft copolymers. This method allows the formation of long side chains and enables stepwise tuning of ionic channel through adjustments of the graft degree. Our membrane, poly(styrene-b-ethylene-co-butylene-b-styrene)-graft-triazole-poly(styrene sulfonic acid) (SEBS-g-TzPSSA, referred to as Click SgP) exhibited a highly ordered, microphase-separated morphology. The Click SgP membranes achieved record-high ion conductivities even at low ion exchange capacity (IEC) values. Their well-defined nanostructure, coupled with extended side chains, provided enhanced mechanical stability and elongation properties while efficiently regulating water uptake and minimizing swelling. Unlike conventional hydrocarbon PEMs, the Click SgP membranes were successfully employed in a large-scale, mass-production-compatible decal transfer method for fabricating membrane electrode assemblies (MEAs). This study explores vapor sorption, ion transport, and electrochemical performance, highlighting the pivotal role of click chemistry in developing advanced nanostructured polymer architectures.

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引用次数: 0

Evaluation of the adsorptive behaviour of kraft black liquor on nanofiltration model membrane surfaces via quartz crystal microbalance with dissipation monitoring (QCM-D)

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-25 DOI: 10.1016/j.memsci.2025.124043

Xiao Xiao , Mariona Battestini-Vives , Frank Lipnizki , Gregor Rudolph-Schöpping

Membrane filtration of kraft black liquor (KBL), a side-stream of the pulp and paper industry, is challenged by membrane fouling caused by its multicomponent complexity. The specific contributions of the components found in KBL to the fouling and the characteristics of the fouling layer that they create has not been investigated. Herein, the adsorptive and desorptive behaviours of KBL ultrafiltration (UF) permeate, along solutions of lignin and of hemicelluloses, were studied in real time using quartz crystal microbalance with dissipation monitoring (QCM-D) at 30 °C and 50 °C. Quartz sensors were coated with a polymer to model a nanofiltration (NF) membrane surface. The results revealed that hemicelluloses adsorbed rapidly, forming a relatively soft layer on the model membrane surface, while lignin adsorbed slowly and formed the most stable fouling layer of the three solutions at 30 °C. The KBL UF permeate layers had softest structure with most of the foulants being rinsed away at 30 °C. At 50 °C, the KBL UF permeate layer before sodium hydroxide (NaOH) rinsing was driven by multicomponent assembly—unlike single-component systems, the adsorbed mass exceeded the sum of individual hemicelluloses and lignin contributions, underscoring temperature-enhanced diffusion and co-deposition. After NaOH rinsing at 50 °C, all the fouling layers were softer, rougher, and more hydrophilic compared to those at 30 °C. Especially, a hybrid fouling layer with the highest surface roughness and the strongest hydrophilicity was created by KBL UF permeate, incorporating scaling-resistant deposits formed by residual sodium salts and crosslinked organics. These findings may provide essential knowledge for improving membrane cleaning efficiency of irreversible fouling caused by KBL UF permeate.

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引用次数: 0

One-step preparation of PVDF‒polydopamine blend ultrafiltration membranes via nonsolvent-induced phase separation and their characterization and antifouling mechanism analysis

IF 8.4 1区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Membrane Science

Pub Date : 2025-03-25 DOI: 10.1016/j.memsci.2025.124029

Rui Miao , Yue Mi , Xin Zhang , Shuang Ge , Jiani Qu , Yifan Yang , Haoxue Ran , Danxi Huang , Lei Wang

To address the existing shortcomings in the polydopamine (PDA) modification of ultrafiltration membranes, in this study, dopamine monomers were directly added to a casting solution, and a low-concentration NaClO solution was used as the coagulation bath to prepare a polyvinylidene fluoride (PVDF)/PDA blend membrane by nonsolvent-induced phase separation. The results revealed that an extremely thin PDA coating formed on the surface and cross-section of the membrane during the phase separation process, which featured a short reaction time, high dopamine utilization efficiency and simple operation. Compared to the PVDF membrane, the hydrophilicity and permeate flux of the PVDF/PDA membrane simultaneously improved, overcoming the trade-off faced by traditional PDA modification methods. The PVDF/PDA blend membrane also exhibited superior mechanical strength and a more negative charge. Moreover, PDA modification weakened the hydrophobic force and strengthened the electrostatic repulsion force between the foulants and the membrane, thereby causing the comprehensive force between the foulants and the membrane to decrease significantly. In turn, the weaker interaction between the foulants and the membrane not only decreased the deposition rate of the foulants onto the PVDF/PDA membrane but also enabled easier peeling off of the accumulated foulants on the membrane during the cleaning process. As a result, the PVDF/PDA blend membrane exhibited excellent anti-fouling ability for organic matter.

针对聚多巴胺（PDA）改性超滤膜存在的不足，本研究将多巴胺单体直接加入浇铸液中，以低浓度NaClO溶液为凝固浴，通过非溶剂诱导相分离法制备聚偏氟乙烯（PVDF）/PDA共混膜。结果表明，在相分离过程中，膜的表面和横截面形成了极薄的 PDA 涂层，具有反应时间短、多巴胺利用效率高、操作简单等特点。与 PVDF 膜相比，PVDF/PDA 膜的亲水性和渗透通量同时得到改善，克服了传统 PDA 改性方法所面临的取舍问题。PVDF/PDA 混合膜还表现出更高的机械强度和更多的负电荷。此外，PDA 改性削弱了污物与膜之间的疏水力，增强了静电斥力，从而使污物与膜之间的综合作用力显著降低。反过来，污物与膜之间的相互作用减弱，不仅降低了污物在 PVDF/PDA 膜上的沉积率，而且在清洗过程中更容易剥离膜上积累的污物。因此，PVDF/PDA 混合膜对有机物具有出色的防污能力。

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引用次数: 0