Pub Date : 2024-10-15DOI: 10.1016/j.memsci.2024.123410
Yuxia Zhang , Haojie Liu , Min Liu , Xiangzhong Li , Yitian Zhang , Hongzhuo Sun , Haifeng Shi , Yuanyuan Feng
It is difficult for sulfonated poly(ether ether ketone) (SPEEK) to possess both high proton conduction and vanadium resistance owing to the degree of sulfonation. Herein, the composite membranes (S/GO-TpTG) with cationic covalent organic nanosheet (TpTG) crosslinked graphene oxide (GO-TpTG) are prepared to enhance selectivity by optimizing the ion transport channels. The GO-TpTG can efficiently transport protons utilizing its cationic porous structure and acid-base pairs' interaction with SPEEK. Meanwhile, it can block vanadium ions through the Donnan exclusion and physical blocking effects. The S/GO-TpTG membrane with 3 wt% GO-TpTG exhibits excellent proton conductivity (82.7 mS cm-1) and selectivity (77.9×10-7 cm2 min-1). The VRFB with this membrane exhibits excellent energy efficiency (88.6 - 81.0 % at 100-200 mA cm-2), cycle durability, and self-discharge time (209.8 h). This study confirms the great potential of GO-COF to balance proton conductivity and vanadium resistance, and provides an effective strategy to optimize proton channels.
{"title":"Enhanced selectivity of SPEEK membrane incorporated covalent organic nanosheet crosslinked graphene oxide for vanadium redox flow battery","authors":"Yuxia Zhang , Haojie Liu , Min Liu , Xiangzhong Li , Yitian Zhang , Hongzhuo Sun , Haifeng Shi , Yuanyuan Feng","doi":"10.1016/j.memsci.2024.123410","DOIUrl":"10.1016/j.memsci.2024.123410","url":null,"abstract":"<div><div>It is difficult for sulfonated poly(ether ether ketone) (SPEEK) to possess both high proton conduction and vanadium resistance owing to the degree of sulfonation. Herein, the composite membranes (S/GO-TpTG) with cationic covalent organic nanosheet (TpTG) crosslinked graphene oxide (GO-TpTG) are prepared to enhance selectivity by optimizing the ion transport channels. The GO-TpTG can efficiently transport protons utilizing its cationic porous structure and acid-base pairs' interaction with SPEEK. Meanwhile, it can block vanadium ions through the Donnan exclusion and physical blocking effects. The S/GO-TpTG membrane with 3 wt% GO-TpTG exhibits excellent proton conductivity (82.7 mS cm<sup>-1</sup>) and selectivity (77.9×10<sup>-7</sup> cm<sup>2</sup> min<sup>-1</sup>). The VRFB with this membrane exhibits excellent energy efficiency (88.6 - 81.0 % at 100-200 mA cm<sup>-2</sup>), cycle durability, and self-discharge time (209.8 h). This study confirms the great potential of GO-COF to balance proton conductivity and vanadium resistance, and provides an effective strategy to optimize proton channels.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123410"},"PeriodicalIF":8.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445700","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 : 2024-10-15DOI: 10.1016/j.memsci.2024.123406
Fei Han , Bangyuan Song , Jun Liu
Membrane distillation, a thermal-membrane coupled technology, shows potential in desalination despite issues with temperature polarization. The conductive heating vacuum membrane distillation (CHVMD) process addresses temperature polarization by incorporating a thermal conducting layer on the feed side to transfer external heat to the membrane/feed interface. However, the internal mechanism is difficult to analyze through experiments. Hence, a three-dimensional computational fluid dynamics model was developed to simulate the process of heat and mass transfer in CHVMD, considering the effects of the thermophysical properties of the substances. The numerical model was utilized to investigate the influence of feed velocity, liquid-film layer thickness, input heat and heat input method on the system performance. Results showed that the temperature polarization inside the system had been effectively alleviated because the thermal conducting layer can centrally transfer external heat to the feed near the membrane. As the feed velocity and liquid-film layer thickness decreased, system flux increased. With only 25 W input heat, system flux can reach 9.32 kg/m2·h, leading to a larger area of concentrated salt distribution on membrane surface and increasing the risk of salt crystal deposition in membrane pores. Furthermore, we proposed the heat input methods with a variable heat flux, which can effectively solve the salt crystallization while further increasing system flux.
膜蒸馏是一种热-膜耦合技术，尽管存在温度极化问题，但在海水淡化方面显示出潜力。传导加热真空膜蒸馏（CHVMD）工艺通过在进料侧加入导热层将外部热量传递到膜/进料界面来解决温度极化问题。然而，内部机制很难通过实验进行分析。因此，考虑到物质热物理性质的影响，开发了一个三维计算流体动力学模型来模拟 CHVMD 的传热和传质过程。利用该数值模型研究了进料速度、液膜层厚度、输入热量和热量输入方法对系统性能的影响。结果表明，由于导热层可以将外部热量集中传递到膜附近的进料中，因此系统内部的温度极化现象得到了有效缓解。随着进料速度和液膜层厚度的减小，系统通量增加。在输入热量仅为 25 W 的情况下，系统通量可达 9.32 kg/m2-h，这导致膜表面盐分集中分布的面积增大，增加了盐晶在膜孔中沉积的风险。此外，我们还提出了热通量可变的热输入方法，在进一步提高系统通量的同时，可有效解决盐结晶问题。
{"title":"Numerical simulations of conductive heating vacuum membrane distillation: Quantitative analysis of shunted heat flows and preventive strategy of salt crystallization","authors":"Fei Han , Bangyuan Song , Jun Liu","doi":"10.1016/j.memsci.2024.123406","DOIUrl":"10.1016/j.memsci.2024.123406","url":null,"abstract":"<div><div>Membrane distillation, a thermal-membrane coupled technology, shows potential in desalination despite issues with temperature polarization. The conductive heating vacuum membrane distillation (CHVMD) process addresses temperature polarization by incorporating a thermal conducting layer on the feed side to transfer external heat to the membrane/feed interface. However, the internal mechanism is difficult to analyze through experiments. Hence, a three-dimensional computational fluid dynamics model was developed to simulate the process of heat and mass transfer in CHVMD, considering the effects of the thermophysical properties of the substances. The numerical model was utilized to investigate the influence of feed velocity, liquid-film layer thickness, input heat and heat input method on the system performance. Results showed that the temperature polarization inside the system had been effectively alleviated because the thermal conducting layer can centrally transfer external heat to the feed near the membrane. As the feed velocity and liquid-film layer thickness decreased, system flux increased. With only 25 W input heat, system flux can reach 9.32 kg/m<sup>2</sup>·h, leading to a larger area of concentrated salt distribution on membrane surface and increasing the risk of salt crystal deposition in membrane pores. Furthermore, we proposed the heat input methods with a variable heat flux, which can effectively solve the salt crystallization while further increasing system flux.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"715 ","pages":"Article 123406"},"PeriodicalIF":8.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142535011","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 : 2024-10-15DOI: 10.1016/j.memsci.2024.123408
Seyed Abdollatif Hashemifard , Mohammad Ali Ghanavatyan , Amir Jangizehi , Hasan Salehi , Alireza Shakeri , Qusay F. Alsalhy , Dhiyaa Al-Timimi , Christoph Bantz , Michael Maskos , Sebastian Seiffert
The present study aims to investigate the properties, identification, and comprehension of the obstacles encountered in the forward osmosis process when utilizing a hydrogel drawing agent (FO-HG). Furthermore, a comparison is made between the FO-HG system and conventional forward osmosis systems employing a salt solution drawing agent. The comparison and evaluation of the swelling process of hydrogel and the kinetics of water penetration are conducted in both un-constrained and constrained states. Furthermore, the investigation and analysis are carried out to determine the presence or absence of internal concentration polarization (ICP) and external concentration polarization (ECP) phenomena. These phenomena are studied in situations with and without mixing, as well as in different orientations of the membrane (FO-mode and PRO-mode). The impact of these phenomena on the water flux of the systems FO-HG and FO-NaCl is also examined. An evaluation is conducted to determine the influence of the amount and size of hydrogel used as a draw agent in the FO-HG system on the water flux. The results of the study reveal that smaller hydrogel particles in the FO-HG system exhibit a higher flux compared to larger particles. Additionally, it is observed that the water flux in PRO-mode is unexpectedly higher when salt water is used as feed solution. This phenomenon can be ascribed to a counter-osmotic effect, originating from the FO state. Despite the high water absorption capacity of hydrogel and its potential as an ideal drawing agent in the forward osmosis process, the results demonstrate that the flux of the FO-HG system is inferior to that of the FO-NaCl system. Finally, the focus is on resolving the low flux issue by suggesting a process involving multiple cycles throughout day and night. We investigate the influence of hydrogel particle size, membrane surface, hydrogel layer thickness, as well as swelling and deswelling time in one cycle. The swelling time displays a peak at an optimal absorption duration, while the deswelling time does not show a similar optimal point, highlighting the difference between swelling and deswelling phenomena. Therefore, the hydrogels' high absorption capacity alone is insufficient for achieving desalination success. The research findings emphasize the high importance of synthesis of a membrane with minimal resistance, enabling a high water flux and suitable selectivity.
{"title":"Challenges of forward osmosis desalination processes using hydrogels as draw agents","authors":"Seyed Abdollatif Hashemifard , Mohammad Ali Ghanavatyan , Amir Jangizehi , Hasan Salehi , Alireza Shakeri , Qusay F. Alsalhy , Dhiyaa Al-Timimi , Christoph Bantz , Michael Maskos , Sebastian Seiffert","doi":"10.1016/j.memsci.2024.123408","DOIUrl":"10.1016/j.memsci.2024.123408","url":null,"abstract":"<div><div>The present study aims to investigate the properties, identification, and comprehension of the obstacles encountered in the forward osmosis process when utilizing a hydrogel drawing agent (FO-HG). Furthermore, a comparison is made between the FO-HG system and conventional forward osmosis systems employing a salt solution drawing agent. The comparison and evaluation of the swelling process of hydrogel and the kinetics of water penetration are conducted in both un-constrained and constrained states. Furthermore, the investigation and analysis are carried out to determine the presence or absence of internal concentration polarization (ICP) and external concentration polarization (ECP) phenomena. These phenomena are studied in situations with and without mixing, as well as in different orientations of the membrane (FO-mode and PRO-mode). The impact of these phenomena on the water flux of the systems FO-HG and FO-NaCl is also examined. An evaluation is conducted to determine the influence of the amount and size of hydrogel used as a draw agent in the FO-HG system on the water flux. The results of the study reveal that smaller hydrogel particles in the FO-HG system exhibit a higher flux compared to larger particles. Additionally, it is observed that the water flux in PRO-mode is unexpectedly higher when salt water is used as feed solution. This phenomenon can be ascribed to a counter-osmotic effect, originating from the FO state. Despite the high water absorption capacity of hydrogel and its potential as an ideal drawing agent in the forward osmosis process, the results demonstrate that the flux of the FO-HG system is inferior to that of the FO-NaCl system. Finally, the focus is on resolving the low flux issue by suggesting a process involving multiple cycles throughout day and night. We investigate the influence of hydrogel particle size, membrane surface, hydrogel layer thickness, as well as swelling and deswelling time in one cycle. The swelling time displays a peak at an optimal absorption duration, while the deswelling time does not show a similar optimal point, highlighting the difference between swelling and deswelling phenomena. Therefore, the hydrogels' high absorption capacity alone is insufficient for achieving desalination success. The research findings emphasize the high importance of synthesis of a membrane with minimal resistance, enabling a high water flux and suitable selectivity.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123408"},"PeriodicalIF":8.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142442258","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}
Pub Date : 2024-10-15DOI: 10.1016/j.memsci.2024.123405
Shiyu Xiao , Yang Cao , Yinhua Wan , Xiaofeng Hang , Jianquan Luo
The development of high-performance nanofiltration (NF) membranes with extreme chemical stability is urgently needed for the recovery of spent lithium. In this study, a series of polyurea membranes with high lithium recovery efficiency and pH stability were fabricated by zone-regulated interfacial polymerization (IP). The reaction inhibitor Cu2+ in the bulk aqueous phase reduces IP intensity by reversibly binding to the amino groups of polyethyleneimine monomers through chelate bonds. Meanwhile, surfactant promote the uniform diffusion of macromolecular aqueous monomers at the phase interface. The milder polymerization reaction and the more stable phase interface endow the polyurea membrane (NF10k PEI-SDS-Cu2+) with higher water permeance (2.1 L m−2 h−1 bar−1), desirable MgCl2 rejection (94.7 %), and excellent fabrication repeatability. Moreover, the membrane demonstrates stable separation selectivity for Co2+/Li+ and SO42−/Li+ under conditions of 0.05 mol L−1 H2SO4 and 2 mol L−1 LiOH, respectively. Our study provides a facile method for constructing NF membranes with extreme pH stability and confirms the feasibility of membrane-based lithium recovery.
{"title":"High-performance polyurea nanofiltration membrane for waste lithium-ion batteries recycling: Leveraging synergistic control of bulk and interfacial monomer diffusion","authors":"Shiyu Xiao , Yang Cao , Yinhua Wan , Xiaofeng Hang , Jianquan Luo","doi":"10.1016/j.memsci.2024.123405","DOIUrl":"10.1016/j.memsci.2024.123405","url":null,"abstract":"<div><div>The development of high-performance nanofiltration (NF) membranes with extreme chemical stability is urgently needed for the recovery of spent lithium. In this study, a series of polyurea membranes with high lithium recovery efficiency and pH stability were fabricated by zone-regulated interfacial polymerization (IP). The reaction inhibitor Cu<sup>2+</sup> in the bulk aqueous phase reduces IP intensity by reversibly binding to the amino groups of polyethyleneimine monomers through chelate bonds. Meanwhile, surfactant promote the uniform diffusion of macromolecular aqueous monomers at the phase interface. The milder polymerization reaction and the more stable phase interface endow the polyurea membrane (NF<sub>10k PEI-SDS-Cu</sub><sup>2+</sup>) with higher water permeance (2.1 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>), desirable MgCl<sub>2</sub> rejection (94.7 %), and excellent fabrication repeatability. Moreover, the membrane demonstrates stable separation selectivity for Co<sup>2+</sup>/Li<sup>+</sup> and SO<sub>4</sub><sup>2−</sup>/Li<sup>+</sup> under conditions of 0.05 mol L<sup>−1</sup> H<sub>2</sub>SO<sub>4</sub> and 2 mol L<sup>−1</sup> LiOH, respectively. Our study provides a facile method for constructing NF membranes with extreme pH stability and confirms the feasibility of membrane-based lithium recovery.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123405"},"PeriodicalIF":8.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441688","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 selective oxidation of methyl glycolate by oxygen is a green route for the synthesis of methyl glyoxylate, which however faces great challenges like the consecutive hydrolysis reaction between methyl glyoxylate and by-product water. Herein, we fabricated an in-situ water separation catalytic membrane reactor (CMR) to suppress the hydrolysis of methyl glyoxylate, which can promptly and preferentially remove water from the reaction system by a hydrophilic NaA membrane. The MoO3@NaA CMR achieved a high methyl glyoxylate selectivity of 84.0 % at 260 °C and 2 bar, being 32.4 % higher than that of the conventional fixed-bed reactor (FBR), while the methyl glycolate conversion was almost the same for both modes. Moreover, the deactivation of the MoO3 catalyst caused by water in CMR was also greatly inhibited, exhibiting excellent stability as compared to FBR. The in-situ water separation strategy in this work contributed to a new concept to improve the selectivity of easily hydrolyzable products.
氧对羟乙酸甲酯的选择性氧化是合成乙醛酸甲酯的一条绿色途径，但它面临着乙醛酸甲酯与副产物水发生连续水解反应等巨大挑战。在此，我们制作了一种原位水分离催化膜反应器（CMR）来抑制乙醛酸甲酯的水解反应，它能通过亲水性 NaA 膜及时、优先地将水从反应体系中去除。在 260 °C 和 2 bar 条件下，MoO3@NaA CMR 的乙醛酸甲酯选择性高达 84.0%，比传统的固定床反应器（FBR）高出 32.4%，而两种模式的乙醇酸甲酯转化率几乎相同。此外，CMR 中水导致的 MoO3 催化剂失活也受到了极大的抑制，与 FBR 相比表现出了极佳的稳定性。这项工作中的原位水分离策略为提高易水解产物的选择性提供了一个新概念。
{"title":"In-situ water separation enhanced methyl glycolate oxidation to methyl glyoxylate by catalytic membrane reactor","authors":"Jia Ding , Shengyu Zhou , Chenglong Qiu, Yuanhao Wu, Yulong Li, Chao Fan, Fangjun Shao, Shengwei Deng, Jianguo Wang","doi":"10.1016/j.memsci.2024.123403","DOIUrl":"10.1016/j.memsci.2024.123403","url":null,"abstract":"<div><div>The selective oxidation of methyl glycolate by oxygen is a green route for the synthesis of methyl glyoxylate, which however faces great challenges like the consecutive hydrolysis reaction between methyl glyoxylate and by-product water. Herein, we fabricated an in-situ water separation catalytic membrane reactor (CMR) to suppress the hydrolysis of methyl glyoxylate, which can promptly and preferentially remove water from the reaction system by a hydrophilic NaA membrane. The MoO<sub>3</sub>@NaA CMR achieved a high methyl glyoxylate selectivity of 84.0 % at 260 °C and 2 bar, being 32.4 % higher than that of the conventional fixed-bed reactor (FBR), while the methyl glycolate conversion was almost the same for both modes. Moreover, the deactivation of the MoO<sub>3</sub> catalyst caused by water in CMR was also greatly inhibited, exhibiting excellent stability as compared to FBR. The in-situ water separation strategy in this work contributed to a new concept to improve the selectivity of easily hydrolyzable products.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123403"},"PeriodicalIF":8.4,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445701","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}
Landfill leachate, with its high concentrations of persistent organic pollutants, salts, heavy metals, and emerging contaminants, presents significant environmental challenges. This study investigated the combination of dielectric barrier discharge (DBD) and ferrate (Fe(VI)) pretreatment technology in landfill leachate treatment, focusing on its effectiveness in enhancing oxidation performance and mitigating membrane fouling. The results indicated that after DBD/Fe(VI) treatment, TOC and UV254 removal efficiencies increased by 44 % and 67 %, respectively. Additionally, the DBD/Fe(VI) system excelled in removing fluorescent substances and high molecular weight organic compounds, thereby reducing the formation of the cake layer on the nanofiltration membrane. This system enhanced oxidation performance through the synergistic production of reactive intermediates, with Fe(V)/Fe(IV) and •OH being the main active species, O2•-, and 1O2 also contributing significantly. The degradation pathway of perfluorooctanoic acid was investigated by utilizing it as the representative pollutant. Compared to the raw landfill leachate system, the DBD/Fe(VI) increased membrane flux by 104 %, while reducing reversible and irreversible fouling resistances by 67 % and 75 %, respectively. Furthermore, the advantages and practical application potential of the DBD/Fe(VI) system were evaluated from energy consumption, economic cost, and carbon dioxide emissions. The study offers an innovative method for landfill leachate treatment and fouling mitigation.
{"title":"Sustainable approach for landfill leachate treatment through dielectric barrier discharge/ferrate (DBD/Fe(VI)) enhanced nanofiltration","authors":"Bin Liu, Danjing Lu, Tianliang Zhang, Yixun Shen, Zhen Qiu, Xin Mao, Ruoxi Wu","doi":"10.1016/j.memsci.2024.123404","DOIUrl":"10.1016/j.memsci.2024.123404","url":null,"abstract":"<div><div>Landfill leachate, with its high concentrations of persistent organic pollutants, salts, heavy metals, and emerging contaminants, presents significant environmental challenges. This study investigated the combination of dielectric barrier discharge (DBD) and ferrate (Fe(VI)) pretreatment technology in landfill leachate treatment, focusing on its effectiveness in enhancing oxidation performance and mitigating membrane fouling. The results indicated that after DBD/Fe(VI) treatment, TOC and UV<sub>254</sub> removal efficiencies increased by 44 % and 67 %, respectively. Additionally, the DBD/Fe(VI) system excelled in removing fluorescent substances and high molecular weight organic compounds, thereby reducing the formation of the cake layer on the nanofiltration membrane. This system enhanced oxidation performance through the synergistic production of reactive intermediates, with Fe(V)/Fe(IV) and •OH being the main active species, O<sub>2</sub><sup>•-</sup>, and <sup>1</sup>O<sub>2</sub> also contributing significantly. The degradation pathway of perfluorooctanoic acid was investigated by utilizing it as the representative pollutant. Compared to the raw landfill leachate system, the DBD/Fe(VI) increased membrane flux by 104 %, while reducing reversible and irreversible fouling resistances by 67 % and 75 %, respectively. Furthermore, the advantages and practical application potential of the DBD/Fe(VI) system were evaluated from energy consumption, economic cost, and carbon dioxide emissions. The study offers an innovative method for landfill leachate treatment and fouling mitigation.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123404"},"PeriodicalIF":8.4,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441686","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 : 2024-10-12DOI: 10.1016/j.memsci.2024.123402
Qian Liu , Kaiwen Wu , Shouhai Zhang , Lin Zhuo , Fanchen Sun , Chenghao Wang , Zijian Li , Yiping He , Yousi Chen , Wei Zhang , Xigao Jian
The trade-off issue between proton conduction properties and stability is a constraint on the commercial application of non-fluorinated proton exchange membranes for fuel cells. To alleviate the issue, the multi-block N-heterocycle poly(aryl ether sulfone)s with ether-free hydrophilic blocks (b-SPDPESs), which is composited by diphenyl sulfone moieties and biphthalazindione structures with dense pendant benzenesulfonic groups, are developed to prepare high-performance membranes. The self-assembly effect of block copolymers not only improves the membrane stability but also constructs regular proton conduction channels. Moreover, the conduction channel consists of hydrophilic blocks without ether bonds, which effectively improves the tolerance of the membrane to radicals. The hydrogen-bond network between sulfonic groups and N-heterocycles in the channel improves the proton conduction efficiency, inhibits the swelling of the membrane, and improves the stability of the membrane. As a result, the swelling degree of b-SPDPESs membrane is only 15.8 %, the proton conductivity is as high as 238 mS cm−1, the membrane aging broken time at 80 °C is between 4 and 6.6 h, and the fuel cells loading the membranes and feeding with hydrogen and air perform the max power density of between 0.65 and 1.25 W cm−2. Modulating the sequence structure of chains and constructing multiblock polymers containing ether-free N-heretrocyclic blocks with sulfonic groups improve the stability of membranes while ensuring their proton conductivity.
质子传导性能与稳定性之间的权衡问题制约了燃料电池非氟质子交换膜的商业应用。为了缓解这一问题，我们开发了具有无醚亲水嵌段的多嵌段 N-杂环聚（芳基醚砜）（b-SPDPES），它由二苯基砜分子和具有致密悬垂苯磺酸基团的双酞嗪二酮结构组成，用于制备高性能膜。嵌段共聚物的自组装效应不仅提高了膜的稳定性，还构建了规则的质子传导通道。此外，传导通道由不含醚键的亲水嵌段组成，这有效提高了膜对自由基的耐受性。通道中磺酸基团和 N-杂环之间的氢键网络提高了质子传导效率，抑制了膜的膨胀，提高了膜的稳定性。因此，b-SPDPESs 膜的溶胀度仅为 15.8%，质子传导率高达 238 mS cm-1，膜在 80 °C 下的老化破碎时间为 4 至 6.6 h，装载膜并输入氢气和空气的燃料电池的最大功率密度为 0.65 至 1.25 W cm-2。调节链的序列结构和构建含有磺酸基的无醚 N-heretrocyclic 嵌段的多嵌段聚合物可提高膜的稳定性，同时确保膜的质子传导性。
{"title":"High-performance proton exchange membrane derived from N-heterocycle poly(aryl ether sulfone)s with ether-free hydrophilic blocks and exhibiting good stability and proton-conducting performance","authors":"Qian Liu , Kaiwen Wu , Shouhai Zhang , Lin Zhuo , Fanchen Sun , Chenghao Wang , Zijian Li , Yiping He , Yousi Chen , Wei Zhang , Xigao Jian","doi":"10.1016/j.memsci.2024.123402","DOIUrl":"10.1016/j.memsci.2024.123402","url":null,"abstract":"<div><div>The trade-off issue between proton conduction properties and stability is a constraint on the commercial application of non-fluorinated proton exchange membranes for fuel cells. To alleviate the issue, the multi-block N-heterocycle poly(aryl ether sulfone)s with ether-free hydrophilic blocks (b-SPDPESs), which is composited by diphenyl sulfone moieties and biphthalazindione structures with dense pendant benzenesulfonic groups, are developed to prepare high-performance membranes. The self-assembly effect of block copolymers not only improves the membrane stability but also constructs regular proton conduction channels. Moreover, the conduction channel consists of hydrophilic blocks without ether bonds, which effectively improves the tolerance of the membrane to radicals. The hydrogen-bond network between sulfonic groups and N-heterocycles in the channel improves the proton conduction efficiency, inhibits the swelling of the membrane, and improves the stability of the membrane. As a result, the swelling degree of b-SPDPESs membrane is only 15.8 %, the proton conductivity is as high as 238 mS cm<sup>−1</sup>, the membrane aging broken time at 80 °C is between 4 and 6.6 h, and the fuel cells loading the membranes and feeding with hydrogen and air perform the max power density of between 0.65 and 1.25 W cm<sup>−2</sup>. Modulating the sequence structure of chains and constructing multiblock polymers containing ether-free N-heretrocyclic blocks with sulfonic groups improve the stability of membranes while ensuring their proton conductivity.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123402"},"PeriodicalIF":8.4,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441687","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 : 2024-10-11DOI: 10.1016/j.memsci.2024.123399
Tsung-Yen Tsou, Jyh-Ping Hsu , Hsiu-Yu Yu
We theoretically investigate the effects of ion adsorption on nanofiltration by simultaneously solving the modified Navier-Stokes, Poisson, and Nernst-Planck equations. Considering the confined space in the nanopore and the layered structure of water near the nanopore surface, hindered transport and anisotropic dielectric exclusion are separately incorporated to demonstrate the corresponding influences on salt rejection. For symmetric electrolytes, ion adsorption decreases the rejection of NaCl slightly but alters the rejection performance of CaSO4 significantly. In particular, ion adsorption improves the rejection of asymmetric electrolytes due to the charge polarity reversal. With ion adsorption, the susceptibility of rejection to pH changes diminishes, and the dependence of rejection on feed concentration decreases. Owing to the counteracting effects of increased surface charge density and more pronounced ion screening as feed concentration rises, the rejection of CaCl2 and Na2SO4 exhibits a maximum under specific pH ranges. 2D surface plots illustrate the dependence of rejection on concentration and pH. In addition, the effect of hindered transport is beneficial to rejection. As the diffusivities of ionic species drop or the diffusivity ratio of co-ions (relative to the surface charge polarity) to counterions decreases, the rejection increases pronouncedly. Lastly, dielectric exclusion in the nanopore results in a more negative surface charge density due to the repulsion of protons from the surface, thereby causing a shift of the isoelectric point towards lower pH values. The effect of the reduction in the perpendicular dielectric permittivity may be enhanced or offset partially by that of the increase in the parallel dielectric permittivity.
{"title":"Unraveling the impact of ion adsorption and dielectric exclusion on nanofiltration through pH-regulated cylindrical nanopores","authors":"Tsung-Yen Tsou, Jyh-Ping Hsu , Hsiu-Yu Yu","doi":"10.1016/j.memsci.2024.123399","DOIUrl":"10.1016/j.memsci.2024.123399","url":null,"abstract":"<div><div>We theoretically investigate the effects of ion adsorption on nanofiltration by simultaneously solving the modified Navier-Stokes, Poisson, and Nernst-Planck equations. Considering the confined space in the nanopore and the layered structure of water near the nanopore surface, hindered transport and anisotropic dielectric exclusion are separately incorporated to demonstrate the corresponding influences on salt rejection. For symmetric electrolytes, ion adsorption decreases the rejection of NaCl slightly but alters the rejection performance of CaSO<sub>4</sub> significantly. In particular, ion adsorption improves the rejection of asymmetric electrolytes due to the charge polarity reversal. With ion adsorption, the susceptibility of rejection to pH changes diminishes, and the dependence of rejection on feed concentration decreases. Owing to the counteracting effects of increased surface charge density and more pronounced ion screening as feed concentration rises, the rejection of CaCl<sub>2</sub> and Na<sub>2</sub>SO<sub>4</sub> exhibits a maximum under specific pH ranges. 2D surface plots illustrate the dependence of rejection on concentration and pH. In addition, the effect of hindered transport is beneficial to rejection. As the diffusivities of ionic species drop or the diffusivity ratio of co-ions (relative to the surface charge polarity) to counterions decreases, the rejection increases pronouncedly. Lastly, dielectric exclusion in the nanopore results in a more negative surface charge density due to the repulsion of protons from the surface, thereby causing a shift of the isoelectric point towards lower pH values. The effect of the reduction in the perpendicular dielectric permittivity may be enhanced or offset partially by that of the increase in the parallel dielectric permittivity.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123399"},"PeriodicalIF":8.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142534732","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 : 2024-10-11DOI: 10.1016/j.memsci.2024.123401
Shude Zhang , Jason Yi Juang Yeo , Jian Song , Basil T. Wong , Jaka Sunarso , Tao Li , Shaomin Liu
Mixed ionic-electronic conducting oxygen transport membranes have demonstrated high oxygen permeability, which can be coupled with other oxidation reactions. The membrane reactor coupling water splitting with partial oxidation of methane reaction has great practical potential as it produces valuable feedstocks such as ammonia syngas and liquid fuel syngas. However, the existing membrane materials often exhibit structural stability issue and/or unsatisfactory oxygen permeability. In this work, copper-doped LCF1-xCuxO3-δ (x = 0.05–0.1) hollow fiber membranes were used for hydrogen production by coupling the oxygen separation with water splitting and partial oxidation of methane. A small amount of copper doping could effectively reduce the sintering temperature of the membrane and increase the conductivity of the material, where a maximum oxygen flux of 0.55 mL min−1 cm−2 was achieved on LCFCu0.05 membrane under the experimental conditions. In the water splitting test, a maximum hydrogen production rate of 3.7 mL min−1 cm−2 was achieved by using steam as the raw gas (driven by nitrogen) at the shell side and hydrogen/helium mixture as the sweep gas at the lumen side of the LCFCu0.05 hollow fiber membrane with 10 wt.% Ni/SDC catalyst coated on the shell side. As pure methane gas was introduced at the lumen side coated with Ni/LaNiO3/γ-Al2O3 catalyst, the H2 production rate was further increased to its highest of 4.4 mL min−1 cm−2. In addition, the membrane reactor could be stably operated for 300 h under three different flow conditions without performance degradation. These results paves the development of robust membrane reactor for integrated water splitting and partial oxidation of methane.
混合离子-电子导电氧传输膜已证明具有很高的透氧性，可与其他氧化反应耦合。将水分离与甲烷部分氧化反应耦合的膜反应器具有巨大的实用潜力，因为它能产生有价值的原料，如合成氨和液体燃料合成气。然而，现有的膜材料往往存在结构稳定性问题和/或透氧性不理想。在这项研究中，掺铜的 LCF1-xCuxO3-δ （x = 0.05-0.1）中空纤维膜被用于制氢，将氧分离与水分裂和甲烷的部分氧化结合起来。少量的铜掺杂可以有效降低膜的烧结温度，提高材料的导电性，在实验条件下，LCFCu0.05 膜的最大氧通量为 0.55 mL min-1 cm-2。在水分裂试验中，以蒸汽为原料气体（由氮气驱动）在壳侧，以氢/氦混合物为扫气在腔侧，LCFCu0.05 中空纤维膜的最大产氢率为 3.7 mL min-1 cm-2，膜壳侧涂有 10 wt.% Ni/SDC 催化剂。当在涂有 Ni/LaNiO3/γ-Al2O3 催化剂的膜腔侧引入纯甲烷气体时，H2 产率进一步提高，最高达到 4.4 mL min-1 cm-2。此外，膜反应器可在三种不同的流动条件下稳定运行 300 小时而不会出现性能下降。这些结果为开发用于集成水分离和甲烷部分氧化的坚固膜反应器铺平了道路。
{"title":"Co-free La0.9Ca0.1Fe1-xCuxO3-δ (x = 0.05, 0.1) hollow fiber membranes for H2/N2 and H2/CO co-production by coupling water splitting and partial oxidation of methane","authors":"Shude Zhang , Jason Yi Juang Yeo , Jian Song , Basil T. Wong , Jaka Sunarso , Tao Li , Shaomin Liu","doi":"10.1016/j.memsci.2024.123401","DOIUrl":"10.1016/j.memsci.2024.123401","url":null,"abstract":"<div><div>Mixed ionic-electronic conducting oxygen transport membranes have demonstrated high oxygen permeability, which can be coupled with other oxidation reactions. The membrane reactor coupling water splitting with partial oxidation of methane reaction has great practical potential as it produces valuable feedstocks such as ammonia syngas and liquid fuel syngas. However, the existing membrane materials often exhibit structural stability issue and/or unsatisfactory oxygen permeability. In this work, copper-doped LCF<sub>1-x</sub>Cu<sub>x</sub>O<sub>3-δ</sub> (x = 0.05–0.1) hollow fiber membranes were used for hydrogen production by coupling the oxygen separation with water splitting and partial oxidation of methane. A small amount of copper doping could effectively reduce the sintering temperature of the membrane and increase the conductivity of the material, where a maximum oxygen flux of 0.55 mL min<sup>−1</sup> cm<sup>−2</sup> was achieved on LCFCu<sub>0.05</sub> membrane under the experimental conditions. In the water splitting test, a maximum hydrogen production rate of 3.7 mL min<sup>−1</sup> cm<sup>−2</sup> was achieved by using steam as the raw gas (driven by nitrogen) at the shell side and hydrogen/helium mixture as the sweep gas at the lumen side of the LCFCu<sub>0.05</sub> hollow fiber membrane with 10 wt.% Ni/SDC catalyst coated on the shell side. As pure methane gas was introduced at the lumen side coated with Ni/LaNiO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> catalyst, the H<sub>2</sub> production rate was further increased to its highest of 4.4 mL min<sup>−1</sup> cm<sup>−2</sup>. In addition, the membrane reactor could be stably operated for 300 h under three different flow conditions without performance degradation. These results paves the development of robust membrane reactor for integrated water splitting and partial oxidation of methane.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123401"},"PeriodicalIF":8.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441689","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}
Pub Date : 2024-10-10DOI: 10.1016/j.memsci.2024.123391
Mariagiulia Longo , Riccardo Mobili , Marcello Monteleone , Sonia La Cognata , Alessio Fuoco , Elisa Esposito , Massimo Boiocchi , Chiara Milanese , Donatella Armentano , Pegah Hajivand , Valeria Amendola , Johannes C. Jansen
Membrane-based gas separation has been recognized as one of the most promising and energy-efficient processes for CO2 capture from industrial gas streams. Remarkably, commercial gas separation membranes typically contain conventional polymers with sub-optimal performance, necessitating the search for better-performing materials. In this work, we developed novel mixed matrix membranes (MMMs) based on the benchmark polyimide Matrimid® 9725 and a soluble poly (ether ether ketone) PEEK-WC. The addition of a zinc-based metal-organic cage (MOC) featuring two calixsalen macrocyclic units significantly improved the transport properties for various gas pairs with an up to 100 % increase in permeability and up to 10 % increase in selectivity at 30 % MOC. SEM and DSC analyses offered valuable insights into the compatibility between the polymer and MOC, revealing excellent dispersion of up to 30 % of MOC with almost complete phase separation from the matrix. The thermal properties and transport properties were successfully described using the Fox equation and the Maxwell model, respectively. Most interestingly, thin film composites (TFCs) performed much better at 3 times higher cage concentrations than the corresponding self-standing thick films because the faster solvent evaporation limited crystal growth to sub-micron size, favouring a fine homogeneous distribution of the MOC in the polymer matrix. Based on their pure and mixed gas permeation, the TFC-MMMs show promise for the future development of new-generation gas separation membranes.
基于膜的气体分离被认为是从工业气体流中捕获二氧化碳的最有前途和最节能的工艺之一。值得注意的是，商用气体分离膜通常含有性能不理想的传统聚合物，因此有必要寻找性能更好的材料。在这项工作中，我们开发了基于基准聚酰亚胺 Matrimid® 9725 和可溶性聚（醚醚酮）PEEK-WC 的新型混合基质膜 (MMM)。添加了锌基金属有机笼（MOC）的混合基膜具有两个钙镁硒大环单元，显著改善了各种气体对的传输性能，在 MOC 含量为 30% 时，渗透性提高了 100%，选择性提高了 10%。SEM 和 DSC 分析为了解聚合物与 MOC 之间的相容性提供了宝贵的信息，结果表明 MOC 的分散性极佳，最高可达 30%，与基体的相分离几乎完全。热特性和传输特性分别用福克斯方程和麦克斯韦模型进行了成功描述。最有趣的是，薄膜复合材料（TFCs）在笼浓度比相应的自立厚膜高 3 倍的情况下性能更佳，这是因为溶剂蒸发速度更快，将晶体生长限制在亚微米级，有利于 MOC 在聚合物基体中的精细均匀分布。基于其纯气体和混合气体渗透性，TFC-MMMs 为未来开发新一代气体分离膜带来了希望。
{"title":"Metal-organic cages in polyimide and polyetheretherketone thin film composite mixed matrix membranes for gas separation","authors":"Mariagiulia Longo , Riccardo Mobili , Marcello Monteleone , Sonia La Cognata , Alessio Fuoco , Elisa Esposito , Massimo Boiocchi , Chiara Milanese , Donatella Armentano , Pegah Hajivand , Valeria Amendola , Johannes C. Jansen","doi":"10.1016/j.memsci.2024.123391","DOIUrl":"10.1016/j.memsci.2024.123391","url":null,"abstract":"<div><div>Membrane-based gas separation has been recognized as one of the most promising and energy-efficient processes for CO<sub>2</sub> capture from industrial gas streams. Remarkably, commercial gas separation membranes typically contain conventional polymers with sub-optimal performance, necessitating the search for better-performing materials. In this work, we developed novel mixed matrix membranes (MMMs) based on the benchmark polyimide Matrimid® 9725 and a soluble poly (ether ether ketone) PEEK-WC. The addition of a zinc-based metal-organic cage (MOC) featuring two calixsalen macrocyclic units significantly improved the transport properties for various gas pairs with an up to 100 % increase in permeability and up to 10 % increase in selectivity at 30 % MOC. SEM and DSC analyses offered valuable insights into the compatibility between the polymer and MOC, revealing excellent dispersion of up to 30 % of MOC with almost complete phase separation from the matrix. The thermal properties and transport properties were successfully described using the Fox equation and the Maxwell model, respectively. Most interestingly, thin film composites (TFCs) performed much better at 3 times higher cage concentrations than the corresponding self-standing thick films because the faster solvent evaporation limited crystal growth to sub-micron size, favouring a fine homogeneous distribution of the MOC in the polymer matrix. Based on their pure and mixed gas permeation, the TFC-MMMs show promise for the future development of new-generation gas separation membranes.</div></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":"714 ","pages":"Article 123391"},"PeriodicalIF":8.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142534653","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}
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