Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport
Abstract Microporous polymer membranes with high solvent permeability are pivotal for upgrading molecular separations in organic solvents, but this remains challenging due to numerous sub‐0.4 nm ultra‐micropores resulting from local tight packing, which limit solvent‐accessibility. Herein, a micropo...
Saved in:
| Main Authors: | , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2025-08-01
|
| Series: | Advanced Science |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/advs.202416748 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849233235025854464 |
|---|---|
| author | Shuang Guo Chuanjie Fang Jiaqi Li Xiaohe Wang Weilin Feng Hukang Guo Ming Xie Yongbing Zhuang Young Moo Lee Liping Zhu |
| author_facet | Shuang Guo Chuanjie Fang Jiaqi Li Xiaohe Wang Weilin Feng Hukang Guo Ming Xie Yongbing Zhuang Young Moo Lee Liping Zhu |
| author_sort | Shuang Guo |
| collection | DOAJ |
| description | Abstract Microporous polymer membranes with high solvent permeability are pivotal for upgrading molecular separations in organic solvents, but this remains challenging due to numerous sub‐0.4 nm ultra‐micropores resulting from local tight packing, which limit solvent‐accessibility. Herein, a microporous polyimide with high intrinsic free volume [PI‐TB‐NDI, naphthalenediimide (NDI) and Tröger's base (TB)] is synthesized for organic solvent nanofiltration. The resulting polymer showed high free volume because of fused aromatic rings and a twisted structure. Aromatic rings enhanced solvent resistance due to strong molecular interaction, but increased detrimental local tight packing as well. To suppress local tight packing without compromising the molecular interactions vital for stability, an ortho‐methyl group is deliberately introduced onto the TB unit to increase both intra‐ and inter‐molecular steric hindrance, imparting an H‐shaped TB‐NDI‐TB molecular stent. On the introduction of ortho‐methyl groups, the sub‐0.4 nm ultra‐micropores are enlarged to ultra‐micropores (0.6–0.7 nm) to give the membrane with rich solvent‐accessible sub‐nanochannels. This resulted in an unprecedented enhancement of solvent permeability, with ethanol permeability 2‐8 times greater than that of state‐of‐the‐art polymer membranes with similar selectivity. These findings advance the design strategy of microporous membranes with well‐tailored free volume without post‐treatments, enabling upscaling and efficient separation of precious species in organic solvents. |
| format | Article |
| id | doaj-art-1b942105467b4f60a7a74a7480c6328d |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-1b942105467b4f60a7a74a7480c6328d2025-08-20T11:56:10ZengWileyAdvanced Science2198-38442025-08-011230n/an/a10.1002/advs.202416748Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent TransportShuang Guo0Chuanjie Fang1Jiaqi Li2Xiaohe Wang3Weilin Feng4Hukang Guo5Ming Xie6Yongbing Zhuang7Young Moo Lee8Liping Zhu9MOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaMOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaMOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaMOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaMOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaMOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaDepartment of Polymer Science and Engineering Department of Chemical Engineering University of Bath Bath BA2 7AY UKState Key Laboratory of Biochemical Engineering Institute of Process Engineering University of Chinese Academy of Sciences Chinese Academy of Sciences Beijing 100190 ChinaDepartment of Energy Engineering College of Engineering Hanyang University Seoul 04763 South KoreaMOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 ChinaAbstract Microporous polymer membranes with high solvent permeability are pivotal for upgrading molecular separations in organic solvents, but this remains challenging due to numerous sub‐0.4 nm ultra‐micropores resulting from local tight packing, which limit solvent‐accessibility. Herein, a microporous polyimide with high intrinsic free volume [PI‐TB‐NDI, naphthalenediimide (NDI) and Tröger's base (TB)] is synthesized for organic solvent nanofiltration. The resulting polymer showed high free volume because of fused aromatic rings and a twisted structure. Aromatic rings enhanced solvent resistance due to strong molecular interaction, but increased detrimental local tight packing as well. To suppress local tight packing without compromising the molecular interactions vital for stability, an ortho‐methyl group is deliberately introduced onto the TB unit to increase both intra‐ and inter‐molecular steric hindrance, imparting an H‐shaped TB‐NDI‐TB molecular stent. On the introduction of ortho‐methyl groups, the sub‐0.4 nm ultra‐micropores are enlarged to ultra‐micropores (0.6–0.7 nm) to give the membrane with rich solvent‐accessible sub‐nanochannels. This resulted in an unprecedented enhancement of solvent permeability, with ethanol permeability 2‐8 times greater than that of state‐of‐the‐art polymer membranes with similar selectivity. These findings advance the design strategy of microporous membranes with well‐tailored free volume without post‐treatments, enabling upscaling and efficient separation of precious species in organic solvents.https://doi.org/10.1002/advs.202416748free volumemicroporous polymer membranesmolecular stentsorganic solvent transport |
| spellingShingle | Shuang Guo Chuanjie Fang Jiaqi Li Xiaohe Wang Weilin Feng Hukang Guo Ming Xie Yongbing Zhuang Young Moo Lee Liping Zhu Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport Advanced Science free volume microporous polymer membranes molecular stents organic solvent transport |
| title | Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport |
| title_full | Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport |
| title_fullStr | Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport |
| title_full_unstemmed | Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport |
| title_short | Microporous Polymer Membranes: Molecular Stents Enhanced Solvent‐Accessibility for Organic Solvent Transport |
| title_sort | microporous polymer membranes molecular stents enhanced solvent accessibility for organic solvent transport |
| topic | free volume microporous polymer membranes molecular stents organic solvent transport |
| url | https://doi.org/10.1002/advs.202416748 |
| work_keys_str_mv | AT shuangguo microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT chuanjiefang microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT jiaqili microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT xiaohewang microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT weilinfeng microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT hukangguo microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT mingxie microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT yongbingzhuang microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT youngmoolee microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport AT lipingzhu microporouspolymermembranesmolecularstentsenhancedsolventaccessibilityfororganicsolventtransport |