Zeolite rings

The position of the metal cation with respect to the zeolite ring depends strongly on the ionic radius of the cation, as is evident from x-ray... 

This system is represented by a closed basin, made of impermeable rocks and filled in the past by a saline alkaline lake. Water in this case could not permeate downwards but only evaporate, so the deposit develops horizontally, instead of vertically as in the previous occurrence. Here pH and salinity in the fluids tend to increase, giving rise to brines, c.g., basic, alkali-rich solutions. Concentric zones of authigenic minerals are so formed, from an outer and upper ring of little altered glass and clay minerals, to zeolites, analcime and a finally alkali-feldspars. A good example for this type of occurrence is Lake Tecopa, California, where the zeolitic ring is constituted by phillipsitc, clinoptilolite and erionite, followed by the central feldspar zone [36]. 

Cluster models for each kind of possible Fe " " single ion stabilization in zeolite are shown in the Fig. 20.36. The first one is a four-membered zeolite ring with two lattice Al +. Silica defect position is simulated as the Fe(0Si)20(0H)4 structure. FeAlO extraframework iron species pseudoshpinel structure FeAl204 was suggested. 

The preferred location of isolated Fe " are six-membered zeolite rings with a symmetric distribution of framework A1 atoms (most stable configurations in Fig. 5). Only a very limited number of cation sites in high-silica zeolite are expected to fulfill these requirements. The... 

Figure C2.12.4. Typical polyhedra found in zeolites (a) sodalite cage found in sodalite, zeolite A or faujasite (b) cancrinite or a-cage found in cancrinite, erionite, offretite or gmelinite (c) the 5-ring polyhedron found in ZSM-5 and ZSM-11 (d) the large cavity of the faujasite stmcture and (e) the a-cage fonning the large cavity in zeolite A.

Wagner P, Yoshikawa M, Lovallo M, Tsu]i K, Tsapatsis and Davis M E 1997 CIT-5 a high-silica zeolite with 14-ring pores Chem. Commun. 2179-80... 

The next step is the ahstraction of a hydride ion hy a Lewis acid site from the zeolite surface to form the more stable allylic carhocation. This is again followed hy a proton elimination to form a cyclohexadiene intermediate. The same sequence is followed until the ring is completely aromatized. 

The importance of quats as structure-directing agents in zeolite synthesis was recently underlined (ref. 5) by the synthesis of the new zeolites SSZ-26 and -33, which combine 10- and 12-ring pores. The templates applied are shown in Figure 3. 

A tetracyclic triquat system has been applied (ref. 6) in the synthesis of ZSM-18, the first known zeolite to contain rings of three (Si, Al)-0 species (3-rings). The structure of ZSM-18 consists of parallel 12-ring channels equipped with side pockets. 

Finally, we mention the use of the polyquat bromide "Dab-4-Br" - easily prepared from Dabco and 1,4-dibromobutane - in the synthesis (ref. 7) of gmelinite (a 1-D 12-ring zeolite). 

The framework structures and pore cross-sections of two types of zeolites are shown. (Top) A Faujasite-type zeolite has a three-dimensional channel system with pores of at least 7.4 A in diameter. A pore is formed by 12 oxygen atoms in a ring. (Bottom) ZSM-5 zeolite has interconnected channels running in one direction, with pores 5.6 A in diameter. ZSM-5 pores are formed by 10 oxygen atoms in a ring. Reprinted with permission from Chemical Engineering Progress, 84(2), February 1988, 32. 

Method B was also used in the preparation of occluded (salen)Cr complexes. ligands Ih and li were prepared within the pores of Cr -exchanged EMT and Y zeolites, respectively [25]. These complexes were tested as catalysts in the ring opening of meso-epoxides with trimethylsilyl azide (Scheme 4). The occluded complexes showed a dramatic decrease in catalytic... 

The problem of accessibility in microporous solids is extreme in zero-dimensional zeolite structures such as clathrasils, that is, zeolite-related materials consisting of window-connected cages. The pore openings in these caged structures are restricted to six-membered rings of [Si04] units at most, which corresponds to pore diameters of approximately 0.2 nm [58]. These pores are too small for the removal of templates and, afterward, are impenetrable to typical sorptive molecules for characterization such as N2 and Ar or reactants such as hydrocarbons. Therefore, the intrinsic... 

The exact nature of the zeolite is determined by the reaction conditions, the silica to alumina ratio and the base used. For example zeolite /3, a class of zeolites with relatively large pores, in the range of 0.7 nm, of which mordenite is an example, are usually made using tetraethylammonium hydroxide as the base. This acts as a template for the formation of 12-membered ring apertures (Figure 4.3). 

Since their development in 1974 ZSM-5 zeolites have had considerable commercial success. ZSM-5 has a 10-membered ring-pore aperture of 0.55 nm (hence the 5 in ZSM-5), which is an ideal dimension for carrying out selective transformations on small aromatic substrates. Being the feedstock for PET, / -xylene is the most useful of the xylene isomers. The Bronsted acid form of ZSM-5, H-ZSM-5, is used to produce p-xylene selectively through toluene alkylation with methanol, xylene isomerization and toluene disproportionation (Figure 4.4). This is an example of a product selective reaction in which the reactant (toluene) is small enough to enter the pore but some of the initial products formed (o and w-xylene) are too large to diffuse rapidly out of the pore. /7-Xylene can, however. 

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