Utilizing mixed surfactants for simultaneous pore templating and active site formation in metal oxides

Self-assembled nonionic alkyl glycoside surfactants are of interest for creating functional adsorption and catalytic sites at the surface of mesoporous metal oxides, but they typically impart poor long-range order when used as pore templates. Improved order and control over the functional site density may be achieved by mixing them with a cationic surfactant. To confirm this hypothesis, we investigate the lyotropic liquid crystalline (LLC) phase behavior of aqueous solutions of the functional nonionic surfactant n-dodecyl beta-D-maltoside (C12G2) and cationic cetyltrimethylammonium bromide (C16TAB). A ternary phase diagram of the C16TAB-C 12G2-water system is developed at 50°C. By replacing the volume of water in the phase diagram with an equivalent volume of silica, ordered mesoporous materials are prepared by nanocasting with variable C 12G2/C16TAB ratios. Metal oxide mesophases can almost always be predicted from the ternary phase diagram, except that silica prepared with high C12G2/C16TAB ratios are very weakly ordered, perhaps due to differences in hydrogen bonding or rate of assembly.;Based on the ternary phase diagram of the system, a systematic approach is taken to the incorporation of titania sites via complexation to the maltoside headgroup of C12G2. Complexation to a saccharide is expected not only to guide titanium to the pore surface, but also to prevent uncontrolled hydrolysis and condensation of the (usually quite reactive) titanium precursor. Tetrahedrally coordinated titanium atoms incorporated into a silica network are believed to be the active oxidation sites required for heterogeneous silica-supported titania oxidation catalysts. To promote well-ordered materials and to allow control over titania site density, the mixed C12G 2 / C16TAB system is used for pore templating. Series of Si-Ti mixed oxide thin films and bulk materials are synthesized with different amounts of titanium loading by utilizing pre-complexation between C12 G2 and titanium isopropoxide. The degrees of homogeneity (indicated by tetracoordinated Ti) in these films are superior to those of films synthesized with the same loading of titanium but without C12G 2 or without pre-complexation. Transition metal-carbohydrate complexation provides highly dispersed, tetrahedrally coordinated titanium atoms rather than the octahedral sites found without saccharide complexation.;KEYWORDS: Mesoporous, mixed surfactant templating, mixed metal oxides, nano-casting, evaporation induced self-assembly...