Mesoporous Ti-SBA-15 has been postsynthesized by the titanation of pure silica SBA-15 in glycerol with the assistance of quaternary organic ammonium hydroxides, and has been extensively characterized by various techniques to investigate the mesostructural and catalytic properties, and the chemical nature of the incorporated Ti species, in comparison with those of Ti-MCM-41. To incorporate tetrahedral Ti species into the silica walls of SAB-15, the titanation needs to be carried out at elevated temperature and using an optimum amount of organic ammonium hydroxide. Ti-SBA-15 samples with a Si/Ti ratio ranging from 376 to 16 are successfully prepared with the retention of hexagonal mesostructure by elaborately conducting the titanation. The nature of the Ti species depends greatly on the Ti loading. At Si/Ti ratios higher than 50, the Ti species are mainly tetrahedrally coordinated in isolated states, while poorly dispersed Ti species of octahedral coordination are formed at higher Ti incorporation levels; however, no anatase phase is formed in all cases. The IR band at 948cm-1 due to Si-O-Ti bonds can be used to characterize the tetrahedral Ti species in mesoporous materials, but the techniques of dehydration or trimethylsilylation should be adopted to get rid of the influence of silanol groups. In an actual catalytic reaction, Ti-SBA-15 exhibits not only extremely high thermal stability but also outstanding endurance against Ti leaching not observed for Ti-MCM-41. Ti-SBA-15 is thus presumed to be a promising liquid-phase oxidation catalyst.

MWW type titanosilicate, Ti-MWW, has been synthesized by the dry-gel conversion (DGC) method, and its physicochemical properties and catalytic performance in the liquid-phase epoxidation of alkene have been compared with that of hydrothermally synthesized (HTS) Ti-MWW. The roles in the crystallization of silica source, alkali cation, cyclic amine as a structure-directing agent (SDA), and boric acid structure-supporting agent have been investigated. The crystallization of Ti-MWW did not occur for the dry gels free of boric acid, but was feasible at a Si/B molar ratio as high as 12 in marked contrast to the ratio of 0.75 required in the hydrothermal synthesis. The sodium as a mineralization agent was not necessary and on the contrary inhibited the crystallization particularly at a high content. The seeding technique using deboronatedMWWeffectively accelerated the crystallization speed and reduced the amount of boric acid required. As-synthesized Ti-MWW-DGC lamellar precursors contained both tetrahedral and octahedral species but the latter was selectively removed by acid treatment. Ti-MWW-DGC catalysts showed lower intrinsic activity than Ti-MWW-HTS in the epoxidation of hex-1-ene with hydrogen peroxide probably because the crystal size of the former was 10-20 times as large as that of the latter and then imposed significant diffusion problems for both the substrates and the products.

The shape selectivity in the liquid-phase hydroxylation of aromatic hydrocarbons with hydrogen peroxide has been studied on two kinds of titanosilicate, the large-pore Ti-M with MOR structure and medium-pore TS-1 with MFI structure, and the liquid-phase diffusion of aromatics into both catalysts was compared in the presence of H2O and H2O2 to clarify the origin of the shape selectivity. The hydroxylation rate on TS-1 decreased monotonically with increasing molecular size in the order benzene>toluene. ethylbenzene>cumene, while Ti-M showed the maximum rate for toluene hydroxylation. The apparent diffusivity of aromatics was lowered roughly by 1 order by adding H2O2 to H2O solvent for both titanosilicates but was not affected for their Ti-free derivatives, mordenite and silicalite-1. The reduction in diffusion rate in the presence of H2O2 was more pronounced for TS-1 and for Ti-rich samples. It is concluded that a bulky Ti peroxo species (Ti-OOH) formed by the interaction of Ti site with H2O2 mainly causes a transition-state shape selectivity in the hydroxylation of bulky aromatics in titanosilicate/H2O2 systems.

Al- and Ga-incorporated ETS-10, designated as ETAlS-10 and ETGaS-10, respectively, were synthesized by using P25 titania as a Ti source. The isomorphous substitution of Al and Ga for framework Si at the (4Si) environment was confirmed by 29Si MASNMR measurements. ETS-10 was more active in the Knoevenagel condensation than Y-type zeolites. The introduction of Al and Ga into ETS-10 enhanced the activity, due to the increase of the ion-exchange sites, which act as Br

Titanosilicate catalysts are of scientific and technological interest because of their ability to be applied to environmentally friendly chemical processes for the liquid-phase catalytic oxidation of a variety of organic compounds, by using H2O2 as a clean oxidant. The medium-sized pore