Issue 10, 2013
From the journal:

Physical Chemistry Chemical Physics

Partially fluorinated MIL-47 and Al-MIL-53 frameworks: influence of functionalization on sorption and breathing properties†

Shyam Biswas,a   Tom Rémy,b   Sarah Couck,b   Dmytro Denysenko,c   Geert Rampelberg,d   Joeri F. M. Denayer,b   Dirk Volkmer,c   Christophe Detavernierd  and  Pascal Van Der Voort*a  

* Corresponding authors

a Dept. of Inorganic and Physical Chemistry, Centre for Ordered Materials, Organometallics and Catalysis, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium
E-mail: pascal.vandervoort@ugent.be
Fax: +32 9 264 49 83
Tel: +32 964 44 42

b Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussel, Belgium

c Institute of Physics, Chair of Solid State and Material Science, Augsburg University, Universitätsstrasse 1, 86135 Augsburg, Germany

d Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, 9000 Ghent, Belgium

Abstract

Two perfluorinated metal hydroxo terephthalates [MIII(OH)(BDC-F)]·n(guests) (MIII = V, MIL-47-F-AS or 1-AS; Al, Al-MIL-53-F-AS or 2-AS) (BDC-F = 2-fluoro-1,4-benzenedicarboxylate; AS = as-synthesized) have been synthesized by a hydrothermal method using microwave irradiation (1-AS) or conventional electric heating (2-AS), respectively. The unreacted or occluded H2BDC-F molecules can be removed under vacuum by direct thermal activation or exchange of guest molecules followed by thermal treatment leading to the empty-pore forms of the title compounds [VIV(O)(BDC-F)] (MIL-47-F, 1) and [AlIII(OH)(BDC-F)] (Al-MIL-53-F, 2). Thermogravimetric analysis (TGA) and temperature-dependent XRPD (TDXRPD) experiments indicate that the compounds are stable up to 385 and 480 °C, respectively. Both of the thermally activated compounds exhibit significant microporosity, as verified by N2, CO2, n-hexane, o- and p-xylene sorption analyses. The structural changes of 2 upon adsorption of CO2, n-hexane, o- and p-xylene were highly influenced due to functionalization by –F groups, as compared to parent Al-MIL-53. The –F groups also introduce a certain degree of hydrophobicity into the frameworks, as demonstrated by the H2O sorption analyses.

Graphical abstract: Partially fluorinated MIL-47 and Al-MIL-53 frameworks: influence of functionalization on sorption and breathing properties

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Article information

DOI
https://doi.org/10.1039/C3CP44204G
Article type
Paper
Submitted
24 Nov 2012
Accepted
09 Jan 2013
First published
10 Jan 2013

Phys. Chem. Chem. Phys., 2013,15, 3552-3561

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Partially fluorinated MIL-47 and Al-MIL-53 frameworks: influence of functionalization on sorption and breathing properties

S. Biswas, T. Rémy, S. Couck, D. Denysenko, G. Rampelberg, J. F. M. Denayer, D. Volkmer, C. Detavernier and P. Van Der Voort, Phys. Chem. Chem. Phys., 2013, 15, 3552 DOI: 10.1039/C3CP44204G

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