Mechanistic Study on Thermally Induced Lattice Stiffening of ZIF-8
© 2021 The Authors. Published by American Chemical Society.
| Veröffentlicht in: | Chemistry of materials : a publication of the American Chemical Society. - 1998. - 33(2021), 11 vom: 08. Juni, Seite 4035-4044 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2021
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| Zugriff auf das übergeordnete Werk: | Chemistry of materials : a publication of the American Chemical Society |
| Schlagworte: | Journal Article |
| Zusammenfassung: | © 2021 The Authors. Published by American Chemical Society. The flexibility of the ZIF-8 aperture, which inhibits a molecular cutoff of 3.4 Å, can be reduced by rapid heat treatment to obtain CO2-selective membranes. However, the early stages of the structural, morphological, and chemical changes responsible for the lattice rigidification remain elusive. Herein, using ex situ and in situ experiments, we determine that a small shrinkage of the unit-cell parameter, ∼0.2%, is mainly responsible for this transformation. Systematic gas permeation studies show that one needs to achieve this shrinkage without a disproportionately large shrinkage in the grain size of the polycrystalline film to avoid the formation of cracks. We show that this condition is uniquely achieved in a short time by exposure of ZIF-8 to a mildly humid environment where lattice parameter shrinkage is accelerated by the incorporation of linker vacancy defects, while the shrinkage in grain size is limited. The water-vapor-led incorporation of linker vacancy defects takes place with an energy barrier of 123 kJ mol-1, much higher than that for the thermal degradation of ZIF-8, <80 kJ mol-1. The latter is promoted by heat treatment in a dry environment at a relatively higher temperature; however, this condition does not shrink the lattice parameters at short exposure time |
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| Beschreibung: | Date Revised 15.06.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 0897-4756 |
| DOI: | 10.1021/acs.chemmater.1c00455 |