Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks
Abstract Flexible metal–organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO2 separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poor...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-42448-3 |
| _version_ | 1797630097446928384 |
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| author | Yuta Sakanaka Shotaro Hiraide Iori Sugawara Hajime Uematsu Shogo Kawaguchi Minoru T. Miyahara Satoshi Watanabe |
| author_facet | Yuta Sakanaka Shotaro Hiraide Iori Sugawara Hajime Uematsu Shogo Kawaguchi Minoru T. Miyahara Satoshi Watanabe |
| author_sort | Yuta Sakanaka |
| collection | DOAJ |
| description | Abstract Flexible metal–organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO2 separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poorly understood despite being crucial to process design. Here, the CO2-induced gate opening of ELM-11 ([Cu(BF4)2(4,4’-bipyridine)2] n ) is investigated by time-resolved in situ X-ray powder diffraction, and a theoretical kinetic model of this process is developed to gain atomistic insight into the transition dynamics. The thus-developed model consists of the differential pressure from the gate opening (indicating the ease of structural transition) and reaction model terms (indicating the transition propagation within the crystal). The reaction model of ELM-11 is an autocatalytic reaction with two pathways for CO2 penetration of the framework. Moreover, gas adsorption analyses of two other flexible MOFs with different flexibilities indicate that the kinetics of the adsorption-induced structural transition is highly dependent on framework structure. |
| first_indexed | 2024-03-11T11:03:10Z |
| format | Article |
| id | doaj.art-51864ddb4d6a40ad895ea667b98cd68d |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-11T11:03:10Z |
| publishDate | 2023-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-51864ddb4d6a40ad895ea667b98cd68d2023-11-12T12:23:46ZengNature PortfolioNature Communications2041-17232023-11-0114111210.1038/s41467-023-42448-3Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworksYuta Sakanaka0Shotaro Hiraide1Iori Sugawara2Hajime Uematsu3Shogo Kawaguchi4Minoru T. Miyahara5Satoshi Watanabe6Department of Chemical Engineering, Kyoto University, NishikyoDepartment of Chemical Engineering, Kyoto University, NishikyoDepartment of Chemical Engineering, Kyoto University, NishikyoDepartment of Chemical Engineering, Kyoto University, NishikyoJapan Synchrotron Radiation Research Institute (JASRI)Department of Chemical Engineering, Kyoto University, NishikyoDepartment of Chemical Engineering, Kyoto University, NishikyoAbstract Flexible metal–organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO2 separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poorly understood despite being crucial to process design. Here, the CO2-induced gate opening of ELM-11 ([Cu(BF4)2(4,4’-bipyridine)2] n ) is investigated by time-resolved in situ X-ray powder diffraction, and a theoretical kinetic model of this process is developed to gain atomistic insight into the transition dynamics. The thus-developed model consists of the differential pressure from the gate opening (indicating the ease of structural transition) and reaction model terms (indicating the transition propagation within the crystal). The reaction model of ELM-11 is an autocatalytic reaction with two pathways for CO2 penetration of the framework. Moreover, gas adsorption analyses of two other flexible MOFs with different flexibilities indicate that the kinetics of the adsorption-induced structural transition is highly dependent on framework structure.https://doi.org/10.1038/s41467-023-42448-3 |
| spellingShingle | Yuta Sakanaka Shotaro Hiraide Iori Sugawara Hajime Uematsu Shogo Kawaguchi Minoru T. Miyahara Satoshi Watanabe Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks Nature Communications |
| title | Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks |
| title_full | Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks |
| title_fullStr | Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks |
| title_full_unstemmed | Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks |
| title_short | Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks |
| title_sort | generalised analytical method unravels framework dependent kinetics of adsorption induced structural transition in flexible metal organic frameworks |
| url | https://doi.org/10.1038/s41467-023-42448-3 |
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