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The flexibility of modified-linker MIL-53 materials
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Munn, Alexis S., Pillai, Renjith, Biswas, Shyam, Stock, Norbert, Maurin, Guillaume and Walton, Richard I. (2016) The flexibility of modified-linker MIL-53 materials. Dalton Transactions, 45 (10). pp. 4162-4168. doi:10.1039/c5dt03438h ISSN 1477-9226.
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Official URL: http://dx.doi.org/10.1039/C5DT03438H
Abstract
The flexibility of eight aluminium hydroxo terephthalates [Al(OH)(BDC–X)]·n(guest) (BDC = 1,4-benzene-dicarboxylate; X = –H, –CH3, –Cl, –Br, –NH2, –NO2, –(OH)2, –CO2H) crystallising in the MIL-53-type structure was investigated upon thermal dehydration of as-made samples, superhydration and methanol adsorption/desorption using in situ powder X-ray diffraction (PXRD). Profile fitting was used to determine lattice parameters as a function of time and/or temperature to describe their structural evolution. It has thus been shown that while methanol vapour adsorption induces an opening of all the modified frameworks, except the –NH2 material, superhydration only leads to open structures for Al-MIL-53–NO2, –Br and –(OH)2. All the MIL-53 solids, except Al-MIL-53–(OH)2 are present in the open structures upon thermal dehydration. In addition to the exploration of the breathing behavior of this MIL-53 series, the issue of disorder in the distribution of the functional groups between the organic linkers was explored. As a typical illustration, density functional theory calculations were carried out on different structures of Al-MIL-53–Cl, in which the distribution of –Cl within two adjacent BDC linkers is varied. The results show that the most energetically stable configuration leads to the best agreement with the experimental PXRD pattern. This observation supports that the distribution of the selected linker substituent in the functionalised solid is governed by energetics and that there is a preference for an ordering of this arrangement.
Item Type: | Journal Article | ||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||
Library of Congress Subject Headings (LCSH): | Porous materials | ||||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||
ISSN: | 1477-9226 | ||||||||||
Official Date: | 16 March 2016 | ||||||||||
Dates: |
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Volume: | 45 | ||||||||||
Number: | 10 | ||||||||||
Number of Pages: | 7 | ||||||||||
Page Range: | pp. 4162-4168 | ||||||||||
DOI: | 10.1039/c5dt03438h | ||||||||||
Status: | Peer Reviewed | ||||||||||
Publication Status: | Published | ||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||
Date of first compliant deposit: | 18 August 2016 | ||||||||||
Date of first compliant Open Access: | 6 October 2016 | ||||||||||
Funder: | Seventh Framework Programme (European Commission) (FP7), Institut universitaire de France, Advantage West Midlands (AWM), European Regional Development Fund (ERDF) | ||||||||||
Grant number: | 228862 (FP7) |
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