We report the synthesis, characterization and catalytic behavior of iron(III) porphyrins immobilized in layered double hydroxides (LDH). A combination of EPR, UV-visible spectroscopy and powder X-ray diffraction (PXRD) was used to characterize the products. Three different procedures were used to perform the immobilization of iron porphyrin: a) adsorption into the LDH powder, b) co-precipitation and c) rehydration of calcined LDH. Several different porphyrins ( Fe ( TSPP ), Fe ( TCPP ), Fe ( TPP ) and Fe ( TDFSPP )) were employed in the study. After characterization, the isolated powders were investigated in the oxidation reaction of cyclohexane by iodosylbenzene and hydrogen peroxide in heterogeneous catalysis in comparison to homogeneous media. Some of these immobilized compounds were very good catalysts for this oxidation reaction, stimulating the future investigation of other substrates.
Crisotila natural e quimicamente modificada foi usada como matrizes para imobilização de ferroporfirinas de segunda geração. As atividades catalíticas dos sólidos obtidos foram avaliadas em reações de oxidação de cicloexano, usando iodosilbenzeno como oxidante. Os resultados de catálise foram analisados e comparados aos obtidos pela imobilização das mesmas ferroporfirinas em sílica funcionalizada com 3-APTS, derivadas do tratamento ácido da crisotila. Os resultados preliminares mostraram que os catalisadores são eficientes e seletivos para a obtenção de álcool.Natural and grafted chrysotile were used as matrices for the immobilization of second generation iron porphyrins. The catalysts obtained were evaluated in the oxidation reaction of cyclohexane, using iodosylbenzene as oxidant agent. The catalyst activity for different conditions was compared with results for the same porphyrins immobilized with 3-APTS grafted disordered silica, obtained from acid-leached chrysotile. Preliminary results have shown that high activity can be obtained with short reaction times, and that the reaction is specific for alcohol.
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