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Issue 20, 2012
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Tuning the catalytic performance of metal–organic frameworks in fine chemistry by active site engineering

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Abstract

The effect of a post-synthetic acid treatment on the catalytic performance of MOFs is evaluated for MIL-100(Fe), an iron-benzenetricarboxylate. The acid-treated frameworks are structurally robust as no differences have been found in XRD patterns after treatment. Porosity of the acid-treated MOFs gradually decreases, most probably as a consequence of anions remaining in the charged frameworks. Monitoring the modification of the MOFs by reactions of which the outcome depends on the acid properties of the catalyst suggests the presence of two types of active sites, with weak Brönsted acid sites in close vicinity to the Lewis acid open metal sites. This is supported by CO-chemisorption experiments which indicate a large increase of both Lewis and Brönsted acidity. In Diels–Alder reactions of oxygenated dienophiles with 1,3-cyclohexadiene, a strong increase of the activity is found for the acid-treated MOFs. This is explained by the enhanced activation of the dienophiles on the modified active sites.

Graphical abstract: Tuning the catalytic performance of metal–organic frameworks in fine chemistry by active site engineering

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Publication details

The article was received on 20 Nov 2011, accepted on 13 Feb 2012 and first published on 28 Mar 2012


Article type: Paper
DOI: 10.1039/C2JM16030G
Citation: J. Mater. Chem., 2012,22, 10313-10321
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    Tuning the catalytic performance of metal–organic frameworks in fine chemistry by active site engineering

    F. Vermoortele, R. Ameloot, L. Alaerts, R. Matthessen, B. Carlier, E. V. R. Fernandez, J. Gascon, F. Kapteijn and D. E. De Vos, J. Mater. Chem., 2012, 22, 10313
    DOI: 10.1039/C2JM16030G

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