TY - JOUR
T1 - The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene
AU - Leus, Karen
AU - Vandichel, Matthias
AU - Liu, Ying Ya
AU - Muylaert, Ilke
AU - Musschoot, Jan
AU - Pyl, Steven
AU - Vrielinck, Henk
AU - Callens, Freddy
AU - Marin, Guy B.
AU - Detavernier, Christophe
AU - Wiper, Paul V.
AU - Khimyak, Yaroslav Z.
AU - Waroquier, Michel
AU - Van Speybroeck, Veronique
AU - Van Der Voort, Pascal
PY - 2012/1
Y1 - 2012/1
N2 - 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.
AB - 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.
KW - DFT-D
KW - Epoxidation
KW - Metal Organic Frameworks
KW - Oxidation catalysis
KW - Vanadium
UR - http://www.scopus.com/inward/record.url?scp=84155162681&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2011.09.014
DO - 10.1016/j.jcat.2011.09.014
M3 - Article
AN - SCOPUS:84155162681
SN - 0021-9517
VL - 285
SP - 196
EP - 207
JO - Journal of Catalysis
JF - Journal of Catalysis
IS - 1
ER -