Iron tetrasulfophthalocyanine (FePcS) has been irreversibly inserted into nanocages of the metal organic framework MIL-101 to give a hybrid material FePcS/MIL-101 which demonstrated a superior catalytic performance in the selective oxidation of aromatic substrates with (t)BuOOH than homogeneous FePcS.

Mesoporous titanium-silicates have been prepared following the evaporation-induced self-assembly (EISA) methodology and characterized by elemental analysis, XRD, N 2 adsorption, SEM, DRS UV-Vis and Raman techniques. The use of acetylacetone during synthesis allowed the formation of highly dispersed dimeric and/or small oligomeric Ti species, within the mesostructured silica network, to be realized. The materials catalyse oxidation of alkylsubstituted phenols to corresponding p-benzoquinones with 100% selectivity using the green oxidant -30% aqueous hydrogen peroxide. The titanium-silicates prepared by the convenient and versatile EISA-based procedure reveal the true heterogeneous nature of the catalysis and do not suffer from titanium leaching. They show advantages over other types of mesoporous Ti,Si-catalysts, such as TiO 2 -SiO 2 mixed oxides and grafted Ti/SiO 2 , in terms of the catalyst stability and reusability.

The surface acidity of different mesoporous titanium-silicates, such as well-organized hexagonally packed Ti-MMM, Ti-MMM-2, Ti-SBA-15, and amorphous TiO(2)-SiO(2) mixed oxides (aerogels and xerogels), was studied by means of FTIR spectroscopy of CO adsorbed at 80 K and CD(3)CN adsorbed at 293 K. The surface hydroxyl groups of mesoporous titanium-silicates with 2-7 wt % Ti revealed a Brönsted acidity slightly higher to that of pure silicate. TiO(2)-SiO(2) xerogels revealed the highest Brönsted acidity among the titanium-silicates studied. CO adsorption revealed two additional sites on the surface in comparison to pure silicate, characterized by nu(CO) from 2185 (high pressure) to 2178 (low pressure) cm(-1) and from 2174 (high pressure) to 2170 (low pressure) cm(-1). These bands are due to CO adsorbed on isolated titanium cations in the silica surrounding or having one Ti(4+) cation in their second coordination sphere and due to CO interactions with Ti-OH groups, respectively. CD(3)CN adsorption similarly revealed the existence of two additional sites, which were not detected for pure silicate: at 2289 cm(-1) due to CD(3)CN interaction with titanol groups and from 2306 (low pressure) to 2300 (high pressure) cm(-1) due to acetonitrile interaction with isolated framework titanium cations with probably one Ti(4+) cation in their second coordination shell. The spectroscopic results are compared with computational data obtained on cluster models of titanium-silicate with different titanium content. According to the IR data, the Ti accessibility on the surfaces for mesoporous titanium-silicates with similar Ti loading (2 wt %) was found to fall in the order TiO(2)-SiO(2) aerogel approximately TiO(2)-SiO(2) xerogel> Ti-MMM approximately Ti-MMM-2 > Ti-SBA-15. This order (except TiO(2)-SiO(2) xerogel) correlates with the catalytic activity found previously for titanium-silicates in 2,3,6-trimethylphenol oxidation with H(2)O(2).

The temperature of methane hydrate dissociation in silica mesopores has been monitored within a wide range of pressures from 10 MPa to 1 GPa. Because the determination of pore size appears to be crucial for the studied phenomenon, several methods of calculation have been applied. According to our findings, the size that corresponds to the mean size of the most representative pores is to be considered as the most reliable. It was concluded that the shape of hydrate particles replicates a host space of pores and may have a complex (e.g., fractal) shape. An attempt to simulate the curvature of hydrate particles by globular (quasi-spherical), elongated (quasi-cylindrical), or any intermediate models has been done. The quasi-spherical model seems to be more adequate for hydrate particles in small pores (<8 nm), while the quasi-cylindrical model fits better the experimental data for hydrate particles in larger pores. According to our experimental results, the hydrate can be formed in pores only by capillary condensate, without involving the water layers tightly bound by the surface, and pressure has an insignificant effect on the decrease of the dissociation temperature of the confined hydrate. A new effect of the formation of hydrates at a temperature higher than the bulk hydrate dissociation temperature has been observed for silica gels with the narrowest pores studied.