New oxidation catalysts based on iron(III) porphyrins immobilized on Mg–Al layered double hydroxides modified with triethanolamine

[Display omitted] ▶ A neutral ironporphyrin was immobilized onto an Mg–Al HDL-NO 3 − (FePor-LDH-N) (a). ▶ A neutral ironporphyrin was immobilized onto Mg–Al–TEA(FePor-LDH-TEA) (b). ▶ Catalytic oxidation of cyclooctene, cyclohexane and heptanes was studied. ▶ Catalytic activity of FePor-LDH-TEA was a...

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Veröffentlicht in:Applied catalysis. A, General General, 2010-09, Vol.386 (1), p.51-59
Hauptverfasser: Castro, Kelly Aparecida Dias de Freitas, Bail, Alesandro, Groszewicz, Pedro Braga, Machado, Guilherme Sippel, Schreiner, Wido Herwig, Wypych, Fernando, Nakagaki, Shirley
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Sprache:eng
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Zusammenfassung:[Display omitted] ▶ A neutral ironporphyrin was immobilized onto an Mg–Al HDL-NO 3 − (FePor-LDH-N) (a). ▶ A neutral ironporphyrin was immobilized onto Mg–Al–TEA(FePor-LDH-TEA) (b). ▶ Catalytic oxidation of cyclooctene, cyclohexane and heptanes was studied. ▶ Catalytic activity of FePor-LDH-TEA was around 5 times higher than FePor-LDH-N. ▶Significant selectivity in the oxidation of heptane was achieved (30.0%). An Mg–Al layered double hydroxide containing intercalated NO 3 − anions (LDH-N) was synthesized and subsequently submitted to a reaction with triethanolamine as modifying agent (LDH-TEA). A neutral iron(III) porphyrin was immobilized onto both solids LDH-N and LDH-TEA, and the catalytic activity of the resulting FePor-LDH-N and FePor-LDH-TEA was evaluated in the oxidation of (Z)-cyclooctene, cyclohexane, and heptane using iodosylbenzene as oxidant. Characterization of FePor-LDH-N and FePor-LDH-TEA by UV–vis, FTIR, XRD, XPS, EPR, TGA/DTA, and SEM was also accomplished. The products from the catalytic reactions were analyzed by GC, using an FID detector. The catalytic activity of FePor-LDH-TEA in the oxidation of cyclohexane was around 5 times higher than that obtained with FePor-LDH-N, which does not contain the modifying agent. Moreover, the FePor-LDH-TEA solid displayed significant selectivity in the oxidation of heptane, a substrate that is difficult to oxidize; in fact, a total product yield over 30.0% was achieved. Finally, the performance of the FePor-LDH-TEA catalyst can be attributed to the higher FePor load in this solid, which is 3 times larger compared with FePor-LDH-N. A proposal concerning the mode of FePor immobilization onto the modified LDH is suggested.
ISSN:0926-860X
1873-3875
DOI:10.1016/j.apcata.2010.07.031