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p-Xylene-Selective Metal–Organic Frameworks: A Case of Topology-Directed Selectivity

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Centre for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Arenbergpark 23, B-3001 Leuven, Belgium
Institut Lavoisier Versailles, UMR 8180, CNRS, Université de Versailles St-Quentin-en-Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
§ Institute for Materials and Processes, School of Engineering, The University of Edinburgh, King’s Buildings, Edinburgh EH9 3JL, United Kingdom
Laboratoire Chimie Provence, UMR 6264, CNRS, Universités d’Aix-Marseille I, II et III, Centre Saint Jérôme, F-13397 Marseille Cedex 20, France
Institute of Inorganic Chemistry, Christian-Albrechts-University, Max-Eyth-Str. 2, D 24118 Kiel, Germany
# Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
Cite this: J. Am. Chem. Soc. 2011, 133, 46, 18526–18529
Publication Date (Web):October 24, 2011
https://doi.org/10.1021/ja207287h
Copyright © 2011 American Chemical Society
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Abstract

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Para-disubstituted alkylaromatics such as p-xylene are preferentially adsorbed from an isomer mixture on three isostructural metal–organic frameworks: MIL-125(Ti) ([Ti8O8(OH)4(BDC)6]), MIL-125(Ti)-NH2 ([Ti8O8(OH)4(BDC-NH2)6]), and CAU-1(Al)-NH2 ([Al8(OH)4(OCH3)8(BDC-NH2)6]) (BDC = 1,4-benzenedicarboxylate). Their unique structure contains octahedral cages, which can separate molecules on the basis of differences in packing and interaction with the pore walls, as well as smaller tetrahedral cages, which are capable of separating molecules by molecular sieving. These experimental data are in line with predictions by molecular simulations. Additional adsorption and microcalorimetric experiments provide insight in the complementary role of the two cage types in providing the para selectivity.

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Experimental procedures; details on microcalorimetry, molecular simulations, and characterization of the materials; and additional figures. This material is available free of charge via the Internet at http://pubs.acs.org.

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