Flexibility versus rigidity: What determines the stability of zeolite frameworks? A case study

E. Verheyen; L. Joos; C. Martineau; C. J. Dawson; C. Weidenthaler; W. Schmidt; R. Yuan; E. Breynaert; V. Van Speybroeck; M. Waroquier; F. Taulelle; M. M.J. Treacy; J. A. Martens; C. E.A. Kirschhock

doi:10.1039/c4mh00127c

Flexibility versus rigidity: What determines the stability of zeolite frameworks? A case study

E. Verheyen, L. Joos, C. Martineau, C. J. Dawson, C. Weidenthaler, W. Schmidt, R. Yuan, E. Breynaert, V. Van Speybroeck, M. Waroquier, F. Taulelle, M. M.J. Treacy, J. A. Martens, C. E.A. Kirschhock

Physics

Research output: Contribution to journal › Article › peer-review

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Abstract

All silica COK-14/-COK-14 with OKO topology is the first case of a zeolite which reversibly transforms from a systematically interrupted to a fully connected state and back. Analysis of the opening/closing behavior allowed the study of entropy and framework flexibility as determinants for the stability of zeolite topologies, which, until now, has been experimentally inaccessible. Interconversion of the all-silica COK-14 zeolite with fully connected OKO topology and its -COK-14 variant with systematic framework interruption was investigated using high-temperature XRD, thermogravimetric analysis, ²⁹Si MAS NMR, nitrogen adsorption and a range of modelling techniques. Specific framework bonds in the OKO framework can be reversibly hydrolyzed and condensed. Structural silanols of the parent -COK-14, prepared by degermanation of the IM-12 zeolite, were condensed by heating at 923 K, and hydrolyzed again to the initial state by contacting the zeolite with warm water. Molecular modelling revealed an inversion of the relative stabilities for both variants depending on temperature and hydration. Condensation of the structural silanols in -COK-14 to COK-14 is entropy driven, mainly resulting from the release of water molecules. Framework reopening in the presence of water is spontaneous due to the high rigidity of the fully connected OKO framework. Isomorphous substitution was demonstrated as a viable option for stabilization of the fully connected OKO framework as this renders the closed framework flexible.

Original language	English (US)
Pages (from-to)	582-587
Number of pages	6
Journal	Materials Horizons
Volume	1
Issue number	6
DOIs	https://doi.org/10.1039/c4mh00127c
State	Published - Nov 2014

ASJC Scopus subject areas

Materials Science(all)
Mechanics of Materials
Process Chemistry and Technology
Electrical and Electronic Engineering

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Verheyen, E., Joos, L., Martineau, C., Dawson, C. J., Weidenthaler, C., Schmidt, W., Yuan, R., Breynaert, E., Van Speybroeck, V., Waroquier, M., Taulelle, F., Treacy, M. M. J., Martens, J. A., & Kirschhock, C. E. A. (2014). Flexibility versus rigidity: What determines the stability of zeolite frameworks? A case study. Materials Horizons, 1(6), 582-587. https://doi.org/10.1039/c4mh00127c

Verheyen, E, Joos, L, Martineau, C, Dawson, CJ, Weidenthaler, C, Schmidt, W, Yuan, R, Breynaert, E, Van Speybroeck, V, Waroquier, M, Taulelle, F, Treacy, MMJ, Martens, JA & Kirschhock, CEA 2014, 'Flexibility versus rigidity: What determines the stability of zeolite frameworks? A case study', Materials Horizons, vol. 1, no. 6, pp. 582-587. https://doi.org/10.1039/c4mh00127c

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abstract = "All silica COK-14/-COK-14 with OKO topology is the first case of a zeolite which reversibly transforms from a systematically interrupted to a fully connected state and back. Analysis of the opening/closing behavior allowed the study of entropy and framework flexibility as determinants for the stability of zeolite topologies, which, until now, has been experimentally inaccessible. Interconversion of the all-silica COK-14 zeolite with fully connected OKO topology and its -COK-14 variant with systematic framework interruption was investigated using high-temperature XRD, thermogravimetric analysis, 29Si MAS NMR, nitrogen adsorption and a range of modelling techniques. Specific framework bonds in the OKO framework can be reversibly hydrolyzed and condensed. Structural silanols of the parent -COK-14, prepared by degermanation of the IM-12 zeolite, were condensed by heating at 923 K, and hydrolyzed again to the initial state by contacting the zeolite with warm water. Molecular modelling revealed an inversion of the relative stabilities for both variants depending on temperature and hydration. Condensation of the structural silanols in -COK-14 to COK-14 is entropy driven, mainly resulting from the release of water molecules. Framework reopening in the presence of water is spontaneous due to the high rigidity of the fully connected OKO framework. Isomorphous substitution was demonstrated as a viable option for stabilization of the fully connected OKO framework as this renders the closed framework flexible.",

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AU - Yuan, R.

AU - Breynaert, E.

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AB - All silica COK-14/-COK-14 with OKO topology is the first case of a zeolite which reversibly transforms from a systematically interrupted to a fully connected state and back. Analysis of the opening/closing behavior allowed the study of entropy and framework flexibility as determinants for the stability of zeolite topologies, which, until now, has been experimentally inaccessible. Interconversion of the all-silica COK-14 zeolite with fully connected OKO topology and its -COK-14 variant with systematic framework interruption was investigated using high-temperature XRD, thermogravimetric analysis, 29Si MAS NMR, nitrogen adsorption and a range of modelling techniques. Specific framework bonds in the OKO framework can be reversibly hydrolyzed and condensed. Structural silanols of the parent -COK-14, prepared by degermanation of the IM-12 zeolite, were condensed by heating at 923 K, and hydrolyzed again to the initial state by contacting the zeolite with warm water. Molecular modelling revealed an inversion of the relative stabilities for both variants depending on temperature and hydration. Condensation of the structural silanols in -COK-14 to COK-14 is entropy driven, mainly resulting from the release of water molecules. Framework reopening in the presence of water is spontaneous due to the high rigidity of the fully connected OKO framework. Isomorphous substitution was demonstrated as a viable option for stabilization of the fully connected OKO framework as this renders the closed framework flexible.

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Flexibility versus rigidity: What determines the stability of zeolite frameworks? A case study

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