The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

Karen Leus, Matthias Vandichel, Ying Ya Liu, Ilke Muylaert, Jan Musschoot, Steven Pyl, Henk Vrielinck, Freddy Callens, Guy B. Marin, Christophe Detavernier, Paul V. Wiper, Yaroslav Z. Khimyak, Michel Waroquier, Veronique Van Speybroeck, Pascal Van Der Voort

Research output: Contribution to journalArticlepeer-review

Abstract

A Metal Organic Framework, containing coordinatively saturated V +IV sites linked together by terephthalic linkers (V-MIL-47), is evaluated as a catalyst in the epoxidation of cyclohexene. Different solvents and conditions are tested and compared. If the oxidant TBHP is dissolved in water, a significant leaching of V-species into the solution is observed, and also radical pathways are prominently operative leading to the formation of an adduct between the peroxide and cyclohexene. If, however, the oxidant is dissolved in decane, leaching is negligible and the structural integrity of the V-MIL-47 is maintained during successive runs. The selectivity toward the epoxide is very high in these circumstances. Extensive computational modeling is performed to show that several reaction cycles are possible. EPR and NMR measurements confirm that at least two parallel catalytic cycles are co-existing: one with V +IV sites and one with pre-oxidized V +V sites, and this is in complete agreement with the theoretical predictions.

Original languageEnglish
Pages (from-to)196-207
Number of pages12
JournalJournal of Catalysis
Volume285
Issue number1
DOIs
Publication statusPublished - Jan 2012
Externally publishedYes

Keywords

  • DFT-D
  • Epoxidation
  • Metal Organic Frameworks
  • Oxidation catalysis
  • Vanadium

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