Kinetics of Guest-Induced Structural Transitions in Metal-Organic-Framework MIL-53(Al)-NH 2 Probed by High-Pressure Nuclear Magnetic Resonance

A nuclear magnetic resonance (NMR) study of a pore opening in amino-functionalized metal-organic framework (MOF) MIL-53(Al) in response to methane pressure variation is presented. Variations of both NMR signal intensities and transversal relaxation rates for methane are found to reveal hysteretic st...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2023-04, Vol.14 (14), p.3391-3396
Main Authors: Zill, Jeremias C, Thompson, Emma S, Nestle, Nikolaus, Valiullin, Rustem
Format: Article
Language:English
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Summary:A nuclear magnetic resonance (NMR) study of a pore opening in amino-functionalized metal-organic framework (MOF) MIL-53(Al) in response to methane pressure variation is presented. Variations of both NMR signal intensities and transversal relaxation rates for methane are found to reveal hysteretic structural transitions in the MOF material, which are smeared out over broad pressure ranges. Experiments with pressure reversals upon an incomplete adsorption/desorption gave deeper insight into the microscopic transition mechanisms. These experiments have unequivocally proven that the non-stepwise pore opening/closing transitions observed in the experiments are governed by a distribution of the opening/closing pressures over different MOF crystallites, for example, due to a distribution of the crystal sizes or shapes. The slow kinetics of the structural transitions measured in the hysteresis regime revealed a complex free energy landscape for the phase transition process.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.3c00155