THE recent synthesis of silica-based mesoporous materials by the cooperative assembly of periodic inorganic and surfactant-based structures has attracted great interest because it extends the range of molecular-sieve materials into the very-large-pore regime. If the synthetic approach can be generalized to transition-metal oxide mesostructures, the resulting nanocomposite materials might find applications in electrochromic or solid-electrolyte devices, as high-surface-area redox catalysts and as substrates for biochemical separations. We have proposed recently6 that the matching of charge density at the surfactant/inorganic interfaces governs the assembly process; such co-organization of organic and inorganic phases is thought to be a key aspect of biomineralization. Here we report a generalized approach to the synthesis of periodic mesophases of metal oxides and cationic or anionic surfactants under a range of pH conditions. We suggest that the assembly process is controlled by electrostatic complementarity between the inorganic ions in solution, the charged surfactant head groups and—when these charges both have the same sign—inorganic counterions. We identify a number of different general strategies for obtaining a variety of ordered composite materials

The organization of cationic or anionic organic and inorganic molecular species to produce three-dimensional periodic biphase arrays is described. The approach uses cooperative nucleation of molecular inorganic solution species with surfactant molecules and their assembly at low temperatures into liquid-crystal-like arrays. The organic/inorganic interface chemistry makes use of four synthesis routes with (S+I-), (S-I+), (S+X-I+), and (S-M+I-) direct and mediated combinations of surfactant (cationic S+, anionic S-) and soluble inorganic (cationic I+, anionic I-) molecular species. The concepts can be widely applied to generate inorganic oxide, phosphate or sulfide framework compositions. Distinct lamellar, cubic silica mesophases were synthesized in a concentrated acidic medium (S+X-I+), with the hexagonal and the cubic phases showing good thermal stability. For the hexagonal mesostructured silica materials high BET surface areas (>1000 m₂/g) are found. Hexagonal tungsten(V1) oxide materials were prepared in the presence of quaternary ammonium surfactants in the pH range 4-8. Cubic (Ia3d) and hexagonal antimony(V) oxides were obtained by acidifying (pH = 6-7) homogeneous solutions of soluble Sb(V) anions and quaternary ammonium surfactants at room temperature (S+I-). Using anionic surfactants, hexagonal and lamellar lead oxide mesostructures were found (S-I+). Crystalline zinc phosphate lamellar phases were obtained at low synthesis temperatures (4°C) and lamellar sulfide phases could be also readily generated at room temperature. The synthesis procedure presented is relevant to the coorganization of organic and inorganic phases in biomineralization processes, and some of the biomimetic implications are discussed

Through a facile one-step combustion method, partially reduced TiO(2) has been synthesized. Electron paramagnetic resonance (EPR) spectra confirm the presence of Ti(3+) in the bulk of an as-prepared sample. The UV-vis spectra show that the Ti(3+) here extends the photoresponse of TiO(2) from the UV to the visible light region, which leads to high visible-light photocatalytic activity for the generation of hydrogen gas from water. It is worth noting that the Ti(3+) sites in the sample are highly stable in air or water under irradiation and the photocatalyst can be repeatedly used without degradation in the activity.

Porous silica, niobia, and titania with three-dimensional structures patterned over multiple length scales were prepared by combining micromolding, polystyrene sphere templating, and cooperative assembly of inorganic sol-gel species with amphiphilic triblock copolymers. The resulting materials show hierarchical ordering over several discrete and tunable length scales ranging from 10 nanometers to several micrometers. The respective ordered structures can be independently modified by choosing different mold patterns, latex spheres, and block copolymers. The examples presented demonstrate the compositional and structural diversities that are possible with this simple approach.Several approaches are currently available for the preparation of ordered structures at different length scales. For example, organic molecular templates can be used to form crystalline zeolite-type structures with ordering lengths less than 3 nm (1); mesoporous materials with ordering lengths of 3 to 30 nm can be obtained using surfactants or amphiphilic block copolymers as structure-directing agents (2-7); the use of latex spheres yields macroporous materials with ordering lengths of 100 nm to 1 m (8 -13); and soft lithography can be used to make high-quality patterns and structures with lateral dimensions of about 30 nm to 500 m (14 -16 ). Despite all of these efforts in nanostructuring materials, the fabrication of hierarchically ordered structures at multiple length scales, such as seen in nature in diatoms (17), has remained an experimental challenge. Such materials are important both for the systematic fundamental study of structure-property relations and for their technological promise in applications such as catalysis, selective separations, sensor arrays, wave guides, miniaturized electronic and magnetic devices, and photonic crystals with tunable band gaps.Previously, micromolding has been used to form patterned mesoporous materials (18,19). These studies, however, used acidic aqueous conditions to carry out the cooperative self-assembly (20), which is disadvantageous because of the limited processibility of the aqueous solutions. Either noncontinuous films were formed (18) or an electric field was needed to guide pattern formation, which requires a nonconducting substrate (19). Latex spheres have also been used to make disordered macro-and mesoporous silica (9). We have developed a simple procedure for preparing hierarchically ordered structures by concurrently or sequentially combining micromolding, latex sphere templating, and cooperative assembly of hydrolyzed inorganic species (metal alkoxides, metal chlorides) and amphiphilic block copolymers. The materials generated from this process exhibit structural ordering at multiple discrete length scales (in this case, 10, 100, and 1000 nm). Patterned macro-and mesoporous materials of various compositions, including silica, niobia, and titania, were synthesized. Such multiple-scale structural organization makes it possible to tune the physical properties of the materials over a wide ...