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Water vapour and gas induced phase transformations in an 8-fold interpenetrated diamondoid metal-organic framework.


ABSTRACT: In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal-organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)2], X-dia-2-Cd, HImibz or 2 = 4-((4-(1H-imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC-SC) transformations between four distinct phases: an as-synthesised (from N,N-dimethylformamide) wide-pore phase, X-dia-2-Cd-α; a narrow-pore phase, X-dia-2-Cd-β, formed upon exposure to water; a narrow-pore phase obtained by activation, X-dia-2-Cd-γ; a medium-pore CO2-loaded phase X-dia-2-Cd-δ. While the space group remained constant in the four phases, the cell volumes and calculated void space ranged from 4988.7 Å3 and 47% (X-dia-2-Cd-α), respectively, to 3200.8 Å3 and 9.1% (X-dia-2-Cd-γ), respectively. X-dia-2-Cd-γ also exhibited a water vapour-induced structural transformation to the water-loaded X-dia-2-Cd-β phase, resulting in an S-shaped sorption isotherm. The inflection point occurred at 18% RH with negligible hysteresis on the desorption profile. Water vapour temperature-humidity swing cycling (60% RH, 300 K to 0% RH, 333 K) indicated hydrolytic stability of X-dia-2-Cd and working capacity was retained after 128 cycles of sorbent regeneration. CO2 (at 195 K) was also observed to induce a structural transformation in X-dia-2-Cd-γ and in situ PXRD studies at 1 bar of CO2, 195 K revealed the formation of X-dia-2-Cd-δ, which exhibited 31% larger unit cell volume than X-dia-2-Cd-γ.

SUBMITTER: Subanbekova A 

PROVIDER: S-EPMC10153660 | biostudies-literature | 2023 May

REPOSITORIES: biostudies-literature

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Water vapour and gas induced phase transformations in an 8-fold interpenetrated diamondoid metal-organic framework.

Subanbekova Aizhamal A   Nikolayenko Varvara I VI   Bezrukov Andrey A AA   Sensharma Debobroto D   Kumar Naveen N   O'Hearn Daniel J DJ   Bon Volodymyr V   Wang Shi-Qiang SQ   Koupepidou Kyriaki K   Darwish Shaza S   Kaskel Stefan S   Zaworotko Michael J MJ  

Journal of materials chemistry. A 20230424 17


In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal-organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)<sub>2</sub>], X-dia-2-Cd, HImibz or 2 = 4-((4-(1<i>H</i>-imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC-SC) transformations between four distinct phases: an as-synthesised (from <i>N</i>,<i>N  ...[more]

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