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The effect of silylation on titanium-containing silica catalysts for the epoxidation of functionalised molecules
Authors:Matteo Guidotti   Isabelle Batonneau-Gener   Enrica Gianotti   Leonardo Marchese   Samuel Mignard   Rinaldo Psaro   Maila Sgobba  Nicoletta Ravasio
Affiliation:

aCNR-ISTM and Centro CIMAINA, via G. Venezian 21, 20133 Milano, Italy

bFaculté des Sciences Fondamentales et Appliquées, Université de Poitiers, UMR CNRS 6503, 40 Av. du Recteur Pineau, 86022 Poitiers Cedex, France

cDip. di Chimica IFM and NIS – Centre of Excellence, Università di Torino, via P. Giuria 7, 10125 Torino, Italy

dDip. di Scienze e Tecnologie Avanzate and Nano-SISTEMI Interdisciplinary Centre, Università del Piemonte Orientale “A. Avogadro”, v. Bellini 25/G, 15100 Alessandria, Italy

eINSTM UdR di Milano, Dip. di Chimica IMA via G. Venezian 21, 20133 Milano, Italy

Abstract:The epoxidation of functionalised substrates of interest as fine chemicals using mesoporous titanium-containing silicas is here reported and the role of silylation in changing the surface hydrophilic character of these catalysts is investigated. The silylation procedure was carried out on two titanium-grafted silicas with different morphologies. An ordered MCM-41 and a non-ordered commercial mesoporous silica were used as supports. The reactivity of bulky substrates with different characteristics (limonene, -terpineol, carveol and methyl linoleate) is studied and compared. The effect of silylation is more pronounced on Ti–MCM-41 than with low-surface area Ti–SiO2 and it is shown that the catalytic performances are strongly dependent on the nature of the reactant. Purely alkenic molecules show better reactivity over silylated catalysts than over non-silylated ones. On the other hand, a hydrophilic environment around the titanium active sites has often a beneficial effect in the epoxidation of richly functionalised substrates.
Keywords:Silylation   Heterogeneous epoxidation catalysts   Hydrophobicity   Hydrophilicity   Titanium   Silica   Unsaturated terpenes   Methyl linoleate
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