Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation
Cage‐like metal–organic frameworks (MOFs) are promising for hexane isomer separation, but their aperture sizes are difficult to control precisely. Herein, a molecular valve strategy is proposed to fine‐tune the aperture of cage‐like MOFs, thereby enhancing their separation performance for hexane iso...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Wiley-VCH
2024-01-01
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| Series: | Small Structures |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/sstr.202300302 |
| _version_ | 1827386723169992704 |
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| author | Rundao Chen Fang Zheng Jiaqi Li Ying Liu Fangru Zhou Haoran Sun Qiwei Yang Zhiguo Zhang Qilong Ren Zongbi Bao |
| author_facet | Rundao Chen Fang Zheng Jiaqi Li Ying Liu Fangru Zhou Haoran Sun Qiwei Yang Zhiguo Zhang Qilong Ren Zongbi Bao |
| author_sort | Rundao Chen |
| collection | DOAJ |
| description | Cage‐like metal–organic frameworks (MOFs) are promising for hexane isomer separation, but their aperture sizes are difficult to control precisely. Herein, a molecular valve strategy is proposed to fine‐tune the aperture of cage‐like MOFs, thereby enhancing their separation performance for hexane isomers. Three novel isostructural cage‐like MOFs, namely Cu‐MO4‐TPA, are synthesized using different oxometallate anions (MO42−, M = Cr, Mo, and W) and the ligand tri(pyridin‐4‐yl)amine (TPA). The different oxometallate anions induce varying degrees of twisting in the TPA ligand, leading to sub‐angstrom tuning in the aperture size of the MOFs. The materials can separate hexane isomers based on their degree of branching, with the smallest aperture material (Cu‐MoO4‐TPA) showing molecular sieving of di‐branched isomers. Adsorption isotherms, kinetic, and breakthrough measurements, Monte Carlo, and density functional theory calculations confirm the aperture size differences result in superior separation of hexane isomers by molecular sieving on Cu‐MoO4‐TPA. The results demonstrate the effectiveness of molecular valve strategy for fine‐tuning MOF aperture size for selective separation applications. |
| first_indexed | 2024-03-08T15:50:41Z |
| format | Article |
| id | doaj.art-5fe43e5b4be44430a66f2cde313e590e |
| institution | Directory Open Access Journal |
| issn | 2688-4062 |
| language | English |
| last_indexed | 2024-03-08T15:50:41Z |
| publishDate | 2024-01-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Small Structures |
| spelling | doaj.art-5fe43e5b4be44430a66f2cde313e590e2024-01-09T05:33:21ZengWiley-VCHSmall Structures2688-40622024-01-0151n/an/a10.1002/sstr.202300302Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer SeparationRundao Chen0Fang Zheng1Jiaqi Li2Ying Liu3Fangru Zhou4Haoran Sun5Qiwei Yang6Zhiguo Zhang7Qilong Ren8Zongbi Bao9Key Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaKey Laboratory of Biomass Chemical Engineering of the Ministry of Education College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Road Hangzhou 310058 P. R. ChinaCage‐like metal–organic frameworks (MOFs) are promising for hexane isomer separation, but their aperture sizes are difficult to control precisely. Herein, a molecular valve strategy is proposed to fine‐tune the aperture of cage‐like MOFs, thereby enhancing their separation performance for hexane isomers. Three novel isostructural cage‐like MOFs, namely Cu‐MO4‐TPA, are synthesized using different oxometallate anions (MO42−, M = Cr, Mo, and W) and the ligand tri(pyridin‐4‐yl)amine (TPA). The different oxometallate anions induce varying degrees of twisting in the TPA ligand, leading to sub‐angstrom tuning in the aperture size of the MOFs. The materials can separate hexane isomers based on their degree of branching, with the smallest aperture material (Cu‐MoO4‐TPA) showing molecular sieving of di‐branched isomers. Adsorption isotherms, kinetic, and breakthrough measurements, Monte Carlo, and density functional theory calculations confirm the aperture size differences result in superior separation of hexane isomers by molecular sieving on Cu‐MoO4‐TPA. The results demonstrate the effectiveness of molecular valve strategy for fine‐tuning MOF aperture size for selective separation applications.https://doi.org/10.1002/sstr.202300302adsorptive separationaperture sizecageshexane isomersmetal–organic frameworks |
| spellingShingle | Rundao Chen Fang Zheng Jiaqi Li Ying Liu Fangru Zhou Haoran Sun Qiwei Yang Zhiguo Zhang Qilong Ren Zongbi Bao Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation Small Structures adsorptive separation aperture size cages hexane isomers metal–organic frameworks |
| title | Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation |
| title_full | Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation |
| title_fullStr | Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation |
| title_full_unstemmed | Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation |
| title_short | Aperture Fine‐Tuning in Cage‐Like Metal–Organic Frameworks via Molecular Valve Strategy for Efficient Hexane Isomer Separation |
| title_sort | aperture fine tuning in cage like metal organic frameworks via molecular valve strategy for efficient hexane isomer separation |
| topic | adsorptive separation aperture size cages hexane isomers metal–organic frameworks |
| url | https://doi.org/10.1002/sstr.202300302 |
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