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This novel molecular sieve was synthesized by hydrothermal reactions of capatal alumina, tetramethylammonium silicate, and sodium silicate in the presence of ionic surfactants It opened a new era of mesoporous materials because of their high surface area (W700 m2 g 1), controllable pore size in a wide range (15 10 nm), and versatile pore surface chemistries Following this pioneering work, material scientists have synthesized mesoporous inorganic networks with different mesostructures (lamellar, two-dimensional (2-D) hexagonal, three-dimensional (3-D) hexagonal, face-centered cubic (FCC), body-centered cubic (BCC), and primitive cubic), using a wide range of surfactants including cationic surfactants (CTAB), anionic surfactants (SDS), nonionic surfactants (Brij 56), and amphiphilic block copolymers (P123), of interest in potential applications in catalysis, membrane separations, adsorption, and chemical sensing Evaporation-Induced Self-Assembly.

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The hydrothermal process designed for MCM-41 is time consuming, and more importantly, the mesoporous products are usually ill-de ned powders that are not transparent, precluding their general applications in thin lms and optical applications Brinker and colleagues developed a new technique denoted as evaporation-induced self-assembly (EISA) to improve the MCM-41 type materials for the fast formation of mesostructured nanoparticles (Lu et al, 1999) and thin lms (Lu et al, 1997) In the EISA process for lm formation during dip-coating, a substrate is dipped into a homogeneous solution of soluble silica, surfactant, water, and acid in ethanol solvent, with an initial surfactant concentration far below the critical micelle concentration (CMC), and withdrawn from the sol solution at a constant speed Preferential evaporation of ethanol concentrates the surfactant, water, acid, and silica species in the depositing lm.

Further evaporation of ethanol concentrates the surfactant to exceed CMC and causes the formation of micelles Beyond this point, progressively increasing surfactant concentration drives self-assembly of silica-surfactant micelles and their organization into highly ordered liquid crystalline mesophases (cubic, hexagonal, or lamellar) that depend on the.

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Figure 13.6. Representative TEM images of mesoporous silica thin lms. Insets are the corresponding electron diffraction patterns.

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composition of surfactant, silica, water, acid, and solvent. After surfactant removal by calcination or solvent extraction, mesoporous silica materials are formed (Fig. 13.6). EISA provides a highly controllable approach to fabricate nanoporous lms and particles. The fast process, easy integration of nanoporous lms into devices, and controllable properties (pore sizes, pore surface chemistries, pore arrangements, and porosity) are especially suitable for the application of nanotechnology in industry.

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