Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn)
Abstract CPO‐27 is a metal‐organic framework (MOF) with coordinatively unsaturated metal centers (open metal sites). It is therefore an ideal host material for small guest molecules, including water. This opens up numerous possible applications, such as proton conduction, humidity sensing, water har...
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Wiley-VCH
2024-12-01
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| Series: | Advanced Materials Interfaces |
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| Online Access: | https://doi.org/10.1002/admi.202400476 |
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| author | Marvin Kloß Michael Beerbaum Dominik Baier Christian Weinberger Frederik Zysk Hossam Elgabarty Thomas D. Kühne Michael Tiemann |
| author_facet | Marvin Kloß Michael Beerbaum Dominik Baier Christian Weinberger Frederik Zysk Hossam Elgabarty Thomas D. Kühne Michael Tiemann |
| author_sort | Marvin Kloß |
| collection | DOAJ |
| description | Abstract CPO‐27 is a metal‐organic framework (MOF) with coordinatively unsaturated metal centers (open metal sites). It is therefore an ideal host material for small guest molecules, including water. This opens up numerous possible applications, such as proton conduction, humidity sensing, water harvesting, or adsorption‐driven heat pumps. For all of these applications, profound knowledge of the adsorption and desorption of water in the micropores is mandatory. The hydration and water structure in CPO‐27‐M (M = Zn or Cu) is investigated using water vapor sorption, Fourier transform infrared (FTIR) spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulation. In the pores of CPO‐27‐Zn, water binds as a ligand to the Zn center. Additional water molecules are stepwise incorporated at defined positions, forming a network of H‐bonds with the framework and with each other. In CPO‐27‐Cu, hydration proceeds by an entirely different mechanism. Here, water does not coordinate to the metal center, but only forms H‐bonds with the framework; pore filling occurs mostly in a single step, with the open metal site remaining unoccupied. Water in the pores forms clusters with extensive intra‐cluster H‐bonding. |
| format | Article |
| id | doaj-art-a645d8820f2d4524b91b45f8584c8fea |
| institution | Kabale University |
| issn | 2196-7350 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Wiley-VCH |
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| series | Advanced Materials Interfaces |
| spelling | doaj-art-a645d8820f2d4524b91b45f8584c8fea2024-12-23T11:32:50ZengWiley-VCHAdvanced Materials Interfaces2196-73502024-12-011135n/an/a10.1002/admi.202400476Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn)Marvin Kloß0Michael Beerbaum1Dominik Baier2Christian Weinberger3Frederik Zysk4Hossam Elgabarty5Thomas D. Kühne6Michael Tiemann7Department of Chemistry – Inorganic Chemistry Faculty of Science Paderborn University Warburger Str. 100 33098 Paderborn GermanyCenter for Advanced Systems Understanding (CASUS) Untermarkt 20 02826 Görlitz GermanyDepartment of Chemistry – Inorganic Chemistry Faculty of Science Paderborn University Warburger Str. 100 33098 Paderborn GermanyDepartment of Chemistry – Inorganic Chemistry Faculty of Science Paderborn University Warburger Str. 100 33098 Paderborn GermanyDepartment of Chemistry – Theoretical Chemistry Faculty of Science Paderborn University Warburger Str. 100 33098 Paderborn GermanyDepartment of Chemistry – Theoretical Chemistry Faculty of Science Paderborn University Warburger Str. 100 33098 Paderborn GermanyCenter for Advanced Systems Understanding (CASUS) Untermarkt 20 02826 Görlitz GermanyDepartment of Chemistry – Inorganic Chemistry Faculty of Science Paderborn University Warburger Str. 100 33098 Paderborn GermanyAbstract CPO‐27 is a metal‐organic framework (MOF) with coordinatively unsaturated metal centers (open metal sites). It is therefore an ideal host material for small guest molecules, including water. This opens up numerous possible applications, such as proton conduction, humidity sensing, water harvesting, or adsorption‐driven heat pumps. For all of these applications, profound knowledge of the adsorption and desorption of water in the micropores is mandatory. The hydration and water structure in CPO‐27‐M (M = Zn or Cu) is investigated using water vapor sorption, Fourier transform infrared (FTIR) spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulation. In the pores of CPO‐27‐Zn, water binds as a ligand to the Zn center. Additional water molecules are stepwise incorporated at defined positions, forming a network of H‐bonds with the framework and with each other. In CPO‐27‐Cu, hydration proceeds by an entirely different mechanism. Here, water does not coordinate to the metal center, but only forms H‐bonds with the framework; pore filling occurs mostly in a single step, with the open metal site remaining unoccupied. Water in the pores forms clusters with extensive intra‐cluster H‐bonding.https://doi.org/10.1002/admi.202400476CPO‐27DFT calculationsmetal‐organic frameworksMOF‐74molecular dynamicsopen metal sites |
| spellingShingle | Marvin Kloß Michael Beerbaum Dominik Baier Christian Weinberger Frederik Zysk Hossam Elgabarty Thomas D. Kühne Michael Tiemann Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn) Advanced Materials Interfaces CPO‐27 DFT calculations metal‐organic frameworks MOF‐74 molecular dynamics open metal sites |
| title | Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn) |
| title_full | Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn) |
| title_fullStr | Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn) |
| title_full_unstemmed | Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn) |
| title_short | Understanding Hydration in CPO‐27 Metal‐Organic Frameworks: Strong Impact of the Chemical Nature of the Metal (Cu, Zn) |
| title_sort | understanding hydration in cpo 27 metal organic frameworks strong impact of the chemical nature of the metal cu zn |
| topic | CPO‐27 DFT calculations metal‐organic frameworks MOF‐74 molecular dynamics open metal sites |
| url | https://doi.org/10.1002/admi.202400476 |
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