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Issue 40, 2013
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Preparation of crystal-like periodic mesoporous phenylene-silica derivatized with ferrocene and its use as a catalyst for the oxidation of styrene

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Abstract

The surface silanol groups in crystal-like mesoporous phenylene-silica have been derivatized with trimethylsilyl, benzyldimethylsilyl and dimethylsilyl(ferrocene) groups by performing a post-synthetic grafting reaction with the corresponding chlorosilane precursors. The success of the grafting procedure was demonstrated by transmission FT-IR spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and 13C and 29Si magic-angle spinning (MAS) NMR spectroscopy. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N2 adsorption data for the modified materials indicated preservation of the mesostructure as well as the molecular-scale periodicity in the pore walls. Ferrocene and the ferrocenyl-modified periodic mesoporous organosilica (PMO) were employed in the catalytic oxidation of styrene at 55 °C using either hydrogen peroxide or tert-butylhydroperoxide as an oxidant. The main reaction product was always benzaldehyde (BzCHO), and other products included styrene oxide, benzoic acid and 2-hydroxyacetophenone. Using a styrene : H2O2 molar ratio of 1 : 5, the highest BzCHO yields at 24 h were 65% (85% selectivity) for ferrocene (semibatch conditions involving stepwise addition of H2O2, 1 mol% Fe) and 34% (83% selectivity) for the modified PMO (batch conditions, 0.06 mol% Fe). The modified PMO could be recovered and reused, albeit with a drop in catalytic activity due to partial metal leaching during the first catalytic run.

Graphical abstract: Preparation of crystal-like periodic mesoporous phenylene-silica derivatized with ferrocene and its use as a catalyst for the oxidation of styrene

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Publication details

The article was received on 16 Jul 2013, accepted on 07 Aug 2013 and first published on 08 Aug 2013


Article type: Paper
DOI: 10.1039/C3DT51931G
Citation: Dalton Trans., 2013,42, 14612-14620
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    Preparation of crystal-like periodic mesoporous phenylene-silica derivatized with ferrocene and its use as a catalyst for the oxidation of styrene

    A. C. Gomes, M. J. Ferreira, S. M. Bruno, N. Bion, P. Ferreira, A. A. Valente, M. Pillinger, J. Rocha and I. S. Gonçalves, Dalton Trans., 2013, 42, 14612
    DOI: 10.1039/C3DT51931G

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