Oxidation of hydrophobic alcohols using aqueous hydrogen peroxide over amphiphilic silica particles loaded with titanium(IV) oxide as a liquid-liquid phase-boundary catalyst

Phase-boundary catalysis (PBC), a new concept of a heterogeneous catalytic system for oxidation of various hydrophobic alcohols with aqueous hydrogen peroxide (H2O2), has been investigated. A part the external surface of silica (SiO2) particles loaded with titanium(IV) oxides was modified with hydrophobic alkyl groups to obtain amphiphilic particles, having both hydrophobic and hydrophilic surfaces on each particle. The amphiphilic particles were spontaneously assembled at interfaces between dual phase mixtures of aqueous solutions and water-immiscible organic compounds. Upon addition to a dual phase mixture of aqueous H2O2 and toluene-containing hydrophobic alcohols, these particles acted as an efficient catalyst for the reaction, to produce corresponding aldehydes and ketones selectively. Notable features of the PBC system are that the oxidation proceeds even without agitation and that only a few percent of titanium species was detected as dissolved species. Productions of aldehydes and ketones were also observed when titanium loaded SiO2 without modification with alkyl groups was employed for the reaction. However, a large amount of titanium loaded on the material was leached during the reaction. These results indicate that surface-covered alkyl groups not only bring about effective contact with hydrophobic alcohols in the organic phase but also give stability against leaching, leading to heterogeneous catalytic functions.