Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks.
Many zeolitic imidazolate frameworks (ZIFs) are promising candidates for use in separation technologies. Comprising large cavities interconnected by small windows they can be used, at least in principle, as molecular sieves where molecules smaller than the window size are able to diffuse into the ma...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 1; pp. 382 - 388 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
1/10/2018
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=127320129&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 127320129 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/10/2018 vid: 140 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 127320129 10.1021/jacs.7b10897 ppf: 382 ppct: 6 formats: tig: atl: Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. aug: au: Hobday, Claire L. Bennett, Thomas D. Jimenez, David Fairen Graham, Alexander J. Morrison, Carole A. Allan, David R. Düren, Tina Moggach, Stephen A. affil: EaStChem School of Chemistry and Centre for Science, Extreme Conditions, University of Edinburgh, David Brewster Road, Joseph Black Building, Edinburgh EH9 3FJ, U.K. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0DZ, U.K. Department of Chemical Engineering & Biotechnology, University of Cambridge, Cambridge CB2 3RA, U.K. Diamond Light Source, Harwell Campus, Didcot OX11 0DE, U.K. Centre for Advanced Separations Engineering, Department of Chemical Engineering, University of Bath, Bath BA2 7AY, U.K. su: Zeolites Imidazoles Metal-organic frameworks Separation (Technology) X-ray diffraction Density functional theory sug: subj: Zeolites Imidazoles Metal-organic frameworks Separation (Technology) X-ray diffraction Density functional theory ab: Many zeolitic imidazolate frameworks (ZIFs) are promising candidates for use in separation technologies. Comprising large cavities interconnected by small windows they can be used, at least in principle, as molecular sieves where molecules smaller than the window size are able to diffuse into the material while larger molecules are rejected. However, "swing effect" or "gate opening" phenomena resulting in an enlargement of the windows have proven to be detrimental. Here, we present the first systematic experimental and computational study of the effect of chemical functionalization of the imidazole linker on the framework dynamics. Using high-pressure (HP) single-crystal X-ray diffraction, density functional theory, and grand canonical Monte Carlo simulations, we show that in the isostructural ZIF-8, ZIF-90, and ZIF-65 functional groups of increasing polarity ( -- CH, -- CHO, and -- NO) on the imidazole linkers provide control over the degree of rotation and thus the critical window diameter. On application of pressure, the substituted imidazolate rings rotate, resulting in an increase in both pore volume and content. Our results show that the interplay between the guest molecules and the chemical function of the imidazole linker is essential for directing the swing effect in ZIF frameworks and therefore the adsorption performance. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2018 holdings: @attributes: islocal: N |
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