Tuning the catalytic performance of metal-organic frameworks in fine chemistry by active site engineering

Frederik Vermoortele, Rob Ameloot, Luc Alaerts, Roman Matthessen, Bert Carlier, Enrique V.Ramos Fernandez, Jorge Gascon, Freek Kapteijn, Dirk E. De Vos*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

121 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)10313-10321
Number of pages9
JournalJournal of Materials Chemistry
Volume22
Issue number20
DOIs
StatePublished - May 28 2012
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry

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