Journal of Catalysis, Vol.163, No.2, 476-488, 1996
Amorphous Microporous Titania-Silica Mixed Oxides - Preparation, Characterization, and Catalytic Redox Properties
Microporous titania-silica mixed oxides with a narrow monomodal pore size distribution at pore diameters of 0.7 nm with highly dispersed titanium in the silica matrix have been obtained by a simple acid-catalyzed sol-gel process in the absence of chelating agents or the prehydrolysis techniques. A mixture of titanium(IV)alkoxide and tetraethoxysilane (TEOS) has been hydrolysed in alcoholic solution with aqueous hydrochloric acid followed by calcination, resulting in amorphous, microporous mixed oxides. There is no limitation on the chemical composition, which covers the whole range from microporous silica to microporous titania. The structural and chemical properties of the materials as a function of preparation parameters (such as acid, titania, or water content, respectively, nature of alcohol, gelation temperature, drying conditions, and titanium source) have been studied by means of physisorption (Ar and N-2), X-ray powder diffraction, spectroscopic techniques, high resolution TEM (in combination with EDX and electron diffraction) and catalytic test reactions (epoxidation of olefins, selective oxidations of saturated hydrocarbons). The high Ti dispersion was negatively affected by changes in the Ti source and/or the alcohol used for the sol-gel process. Increasing BET surface areas were detected as function of the Si/Ti ratio at an optimum in acid concentration. The Si-excess materials stayed X-ray amorphous up to 1173 K. FTIR studies after pyridine treatment showed the materials having weak acidity only. With increasing Ti content an increase in Ti-O-Ti connectivity is observed by DRIFT spectroscopy, resulting in a decrease in epoxidation activity. The glasses show not only catalytic activity for selective oxidation reactions with TBHP comparable with that of other titania containing materials, but size selective epoxidations of olefins are interpreted as shape selectivity resulting from their distinct microporosity. Competitive adsorption experiments of water and octane suggest the hydrophilicity of the amorphous oxides to be the major difference in comparison to their zeolitic analogues.
Keywords:SOL-GEL PROCESS;SURFACE-ACIDITY;TIO2/SIO2 GLASSES;HYDROGEN-PEROXIDE;METAL-OXIDES;TIO2-SIO2;OXIDATION;MICROSTRUCTURE;PRECURSORS;ALKOXIDES