Metal oxides, template-directed

There are, however, two limitations associated with preparation and application of zeolite based catalysts. First, hydrothermal syntheses Umit the extent to which zeolites can be tailored with respect to intended appUcation. Many recipes involving metals that are interesting in terms of catalysis lead to disruption of the balance needed for template-directed pore formation rather than phase separation that produces macroscopic domains of zeoUte and metal oxide without incorporating the metal into the zeohte. When this happens, the benefits of catalysis in confined chambers are lost. Second, hydrothermal synthesis of zeoHtic, silicate based soHds is also currently Hmited to microporous materials. While the wonderfully useful molecular sieving abihty is derived precisely from this property, it also Hmits the sizes of substrates that can access catalyst sites as weU as mass transfer rates of substrates and products to and from internal active sites. 

Among the many desirable properties that are obtained with sol-gel formed metal oxide materials, it is perhaps the hydrophilic/hydrophobic duality of the matrix that allows the successful imprinting of molecular species. In the formation of the gel, templates will direct the placement of siloxane and silanol groups to complementarily interact with various hydrophobic and hydrophilic sites on the template. Figure 8.4 shows a possible form of an imprinted site for propyl orange in a silica matrix. Various aspects of molecular imprinting, such as these concepts, will be explored in the following sections. 

Some important metal oxide materials that have used molecular and supramole-cular templates to direct structure formation are the zeolites and related semi-crystalline aluminosilicates. In this section we shall discuss the use of ammonium cations that direct formation of microporous zeolites and finish with some of the possibilities that exist with the use of surfactant systems and molecular aggregates to create mesoporous structure. Excellent books and reviews are suggested for additional reading into the detailed description of the art [58-60]. The intention of this section is to briefly introduce this area and describe the types of materials being produced using various imprinting techniques in metal oxide materials. 

Complexation/decomplexation of metal ions or of neutral organic molecules, protonation/deprotonation reactions, and oxidation/reduction processes can all be exploited to alter reversibly the stereoelectronic properties of one of the two recognition sites, thus affecting its ability to sustain noncovalent bonds [30-34, 41]. These kinds of switchable [2 catenanes can be prepared following the template-directed synthetic strategy illustrated in Figure 5, wherein one of the two macrocyclic components is preformed and then the other one is clipped around it with the help of noncovalent bonding interactions. 

In the S I+ direct-synthesis pathway, anionic surfactants are used as templates for mesoporous metal oxides. For example, C12H25OSOT Na+ (SDS) as template for A1203 and Ga203 mesoporous materials with Ali3[A104Ali2(0H)24(H20)i27+] and Gai3-Keg-gin [Ga04Ali2(0H)24(H20)127+] as A1 and Ga source, respectively.11841... 

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