Green approaches via nanocatalysis with nanoporous materials: Functionalization of mesoporous materials for single site catalysis

Among the various green keys, catalysis, especially using heterogeneous catalysts, has been powerfully applied to achieve greener chemical processes. Here are presented nanoporous materials which have mesoporosity with the functional groups on the inner pore walls. The materials were synthesized via a rather greener process, such as microwave synthesis, and over these nanocatalysts some of the green chemical reactions were carried out with high activities and selectivities. Cobalt species has been successfully functionalized and stabilized as a Co(III) complex onto SBA-15 support and proven to be an active catalyst in alkylaromatic oxidation with molecular oxygen, styrene epoxidation with tert-butyl hydroperoxide (TBHP), and allylic oxidation of cycloolefins with H₂O₂. Short-channeled amino-functionalized SBA-15 catalyst with hexagonal plate morphology was synthesized directly by using microwave synthesis from the co-condensation of aminopropyl triethoxysilane (APTES) and sodium metasilicate under a strong acidic condition. The catalyst showed high catalytic activity in liquid-phase Knoevenagel condensation reactions, due to easy diffusion and mass transfer of substrates into the short mesopore channel. The HO₃S–SBA-15 was prepared by grafting of mercaptopropyl trimethoxysilane onto the calcined mesoporous silica surface and subsequently oxidized with H₂O₂. The resulting catalyst was applied as a Bronsted solid-acid catalyst for the esterification of oleic acid with methanol.