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
Single-file diffusion is the restricted propagation of particles that cannot pass each other. The occurrence of this phenomenon should be reflected by a change in the time dependence of the mean particle displacement in comparison with ordinary diffusion. Although this process is considered to be the rate-controlling mechanism in a large variety of processes, so far no direct evidence of this phenomenon has been provided. Diffusion measurements made with pulsed field gradient nuclear magnetic resonance (NMR) in unidimensional pore systems (zeolites AlPO4-5 and Theta-1) reflect the expected time dependence of single-file diffusion.
The use of surfactants as templates allows the synthesis of mesostructured transition-metal oxides by a cooperative, interface controlled condensation process
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