Effect of the SiO2/TiO2 ratio on the solid acidity of SiO2-TiO2/montmorillonite composites

SiO₂-TiO₂/montmorillonite composites with varying SiO₂/TiO₂ molar ratios were synthesized and the effect of the SiO₂/TiO₂ ratio on the solid acidity of the resulting composites was investigated. Four composites with SiO₂/TiO₂ molar ratios of 0, 0.1, 1 and 10 were synthesized by the reaction of colloidal SiO₂-TiO₂ particles prepared from alkoxides with sodium-montmorillonite at room temperature. The composites showed slight expansion and broadening of the XRD basal reflection, corresponding to the intercalation of fine colloidal SiO₂-TiO₂ particles into the montmorillonite sheets and incomplete intercalation to form disordered stacking of exfoliated montmorillonite and colloidal SiO₂-TiO₂ particles. The colloidal particles crystallized to anatase in the low SiO₂/TiO₂ composites but remained amorphous in the high SiO₂/TiO₂ composites. The specific surface areas (S_BET) of the composites measured by N₂ adsorption ranged from 250 to 370 m²/g, considerably greater than in montmorillonite (6 m²/g). The pore size increased with decreasing SiO₂/TiO₂ molar ratio of the composites. The NH₃-TPD spectra of the composites consisted of overlapping peaks, corresponded to temperatures of about 190 and 290 °C. The amounts of solid acid obtained from NH₃-TPD were 186-338 μmol/g in the composites; these values are higher than in the commercial catalyst K10 (85 μmol/g), which is synthesized by acid-treatment of montmorillonite. The present sample with SiO₂/TiO₂ = 0.1 showed the highest amount of acid, about four times higher than K10.