Preparation of manganese oxide immobilized on SBA-15 by atomic layer deposition as an efficient and reusable catalyst for selective oxidation of benzyl alcohol in the liquid phase

Manganese oxide supported on mesoporous silica SBA-15 catalyst (Mn-SBA-15) was tested with Mn contents in the range of 0.8–23 wt%. Samples were prepared by the controlled grafting process of atomic layer deposition (ALD). Other sample was prepared for comparisons by the wet impregnation method. These samples were characterized by the techniques of ICP, XRD, SEM, Raman, FT-IR spectroscopy, diffuse reflectance UV–Vis, TGA-DSC, and N₂ absorption–desorption surface area measurement. Results indicated that anchored manganese oxide particles have been successfully synthesized over the surface of SBA-15. These samples contained Red-Ox ion pairs of Mn²⁺ and Mn³⁺ highly dispersed on the mesoporous silica surface. The impregnated sample exhibited lower surface area and contained Red-Ox ion pairs of Mn³⁺ and Mn⁴⁺ more aggregated particles on the SBA-15 surface. Results determined Mn-SBA-15 as an efficient and selective catalyst for oxidation of benzyl alcohol with tert-butylhydroperoxide in liquid phase. In accordance with expectations, there was a negligible amount of leaching of immobilized manganese oxide from the support during the reaction, because of strong surface interaction between manganese oxide and hydroxyls groups. The influences of reaction temperature, reaction time, solvent, TBHP/benzyl alcohol molar ratio, amount of catalyst and reusability were investigated. Under optimized conditions (0.2 g catalyst, TBHP/benzyl alcohol molar ratio 1, solvent acetonitrile; T = 90 °C; reaction time 8 h), results achieved 70% conversion of benzyl alcohol and 100% selectivity to benzaldehyde. - Highlights: • Manganese oxide immobilized on SBA-15 were prepared by atomic layer deposition (ALD). • Oxidation of benzyl alcohol to benzaldehyde over this catalyst were investigated. • Effects of loading of manganese oxide, T, oxidant/alcohol ratio were investigated. • The leaching of manganese oxide from support during the reaction was negligible. • Under optimized conditions 70% Conversion. of alcohol and 100% selectivity to benzaldehyde was achieved