Isomorphous substitution zeolites

Influence of the nature of T atoms on the morphology and crystal size of KZ-2 and ZSM-22 zeolites isomorphously substituted with A1 or Fe... 

Syntheses of KZ-2 and ZSM-22 zeolites isomorphously substituted with iron or aluminium were carried out for a wide range of the Si/T ratio (T=Al, Fe). Effect of the gel composition on size and morphology of the crystals formed was studied. It has been shown that using diethylamine as a template it is possible to synthesize iron containing KZ-2 zeolites with the similar crystals (in size and morphology) independently of Si/Fe ratio in gel. No such effect was observed when the syntheses were carried out in the presence of aluminium in the gel. The results point to an important role of the nature of T cations in the process of the zeolite crystal growth. 

Figure 2.16 Hydroxyl stretching region of FTIR spectra of ZSIVI-5 zeolites isomorphously substituted with iron, gallium, or aluminum. The position of the bridging hydroxyls is labeled. Reproduced with permission from Ref. (99). Copyright 1985 American Chemical Society.

The isomorphic substituted aluminum atom within the zeolite framework has a negative charge that is compensated by a counterion. When the counterion is a proton, a Bronsted acid site is created. Moreover, framework oxygen atoms can give rise to weak Lewis base activity. Noble metal ions can be introduced by ion exchanging the cations after synthesis. Incorporation of metals like Ti, V, Fe, and Cr in the framework can provide the zeolite with activity for redox reactions. 

An extremely versatile catalyst for a variety of synthetically useful oxidations with aqueous hydrogen peroxide is obtained by isomorphous substitution of Si by Ti in molecular sieve materials such as silicalite (the all-silica analogue of zeolite ZSM-5) and zeolite beta. Titanium(IV) silicalite (TS-1), developed by Enichem (Notari, 1988), was the progenitor of this class of materials, which have become known as redox molecular sieves (Arends et al., 1997). 

Montmorillonite is a laminar and expandable clay with wet binding properties and widely available throughout the world. The layers have permanent negative charges due to isomorphic substitutions. The scientific interest of montmorillonite lies in its physical and chemical properties as well as its low price. Consequently, the industrial application of montmorillonite is an attractive process [1]. On the other hand, among numerous reports published so far, crystallization of zeolite Beta draws much attention because of its unique characteristics, in particular, acidity and acid catalysis. It is reasonable to conceive that a catalyst system based on Beta/montmorillonite composite with suitable composition should provide a good catalytic capacity. 

The catalyst samples were prepared in our laboratory. The synthesized Na-ZSM-5 zeolite was modified by conventional or solid state ion-exchange [11] to form H-, Fe-, Cu-, Ni- and Ti-ZSM5 samples, while the mesoporous catalysts (Fe- and Ti-MCM-41) were synthesized by isomorphous substitution [12], as well as the hydrotalcites containing Fe-, Cu-, Cr- or Ca-oxide in the Mg,Al-LDH structure [13]. 

The ZSM5 (Si/Al=40) as base zeolite was prepared by us. Cu was built in the framework by solid phase ion-exchange, Cr by conventional ion-exchange. Ni-samples were obtained by both methods. Ti-ZSM5 was synthesized by isomorphic substitution [8]. 

Macedo et al. [227] studied HY zeolites dealuminated by steaming, and found that the strength of intermediate sites decreased with increasing dealumination for Si/Al ratios varying from 8 to greater than 100. For comparison, isomorphously substituted HY, which is free of extra-framework cationic species, possesses more acid sites than conventionally dealuminated solids with a similar framework Si/Al ratio [227], This is because some of the extra-framework aluminum species act as charge-compensating cations and therefore decrease the number of potential acid sites. 

Extensive studies of the acidity and basicity of zeolites by adsorption calorimetry have been carried out over the past decades, and many reviews have been published [62,64,103,118,120,121,145,146,153,154]. For a given zeolite, different factors can modify its acidity and acid strength the size and strength of the probe molecule, the adsorption temperature, the morphology and crystallinity, the synthesis mode, the effect of pretreatment, the effect of the proton exchange level, the Si/Al ratio and dealumination, the isomorphous substitution, chemical modifications, aging, and coke deposits. 

Changes In shape selectivity due to the Isomorphous substitution of A1 by the larger Fe has not, so far, been unequivocally been established. However, differences in catalytic activity, selectivity and stability between alumino- and ferrisillcate zeolites arising from the presence of weaker... 

A unique titanium(IV)-silica catalyst prepared by impregnating silica with TiCLt or organotitanium compounds exhibits excellent properties with selectivities comparable to the best homogeneous molybdenum catalysts.285 The new zeolite-like catalyst titanium silicalite (TS-1) featuring isomorphous substitution of Si(IV) with Ti(IV) is a very efficient heterogeneous catalyst for selective oxidations with H2C>2.184,185 It exhibits remarkable activities and selectivities in epoxidation of simple olefins.188,304-306 Propylene, for instance, was epoxidized304 with 97% selectivity at 90% conversion at 40°C. Shape-selective epoxidation of 1- and 2-hexenes was observed with this system that failed to catalyze the transformation of cyclohexene.306 Surface peroxotitanate 13 is suggested to be the active spe-... 

Difluorobenzenes are isomerized under gas-phase conditions in the presence of metallosilicates, containing the structure of pentasil zeolites with isomorphic substitution of some silicon atoms by aluminum, gallium, or iron.4 A German patent describes the isomerization of l-bromo-2,4-difluorobenzene to l-bromo-3,5-difluorobenzene in pentasil-type zeolites in an autoclave at 320 C and 25 x 105 Pa for 1 h, giving 29% conversion and 73% selectivity.5... 

From a mechanistic viewpoint it is worth noting that the TS-1 catalyst contains the same chemical elements in roughly the same proportions as the Shell amorphous TiIV/Si02 catalyst referred to earlier. However, the former displays a much broader range of activities than the latter. A possible explanation may be that the TS-1 catalyst contains more (or more active) isolated titanyl centres than the amorphous Ti1v/Si02. Based on the quite remarkable results obtained with TS-1 we expect many more examples of redox zeolites, i.e. zeolites, alpos, etc. modified by isomorphous substitution with redox metal ions in the crystal lattice, as selective oxidation catalysts.66... 

The synthesis of these titanium-substituted zeolites has been described to occur by a secondary synthesis process involving the reaction of [NH4]2TiF6 with the preformed corresponding zeolite (Section IV.G). The chemical and physicochemical properties described are not sufficient to establish the presence of Tiiv ions in framework positions. The titanium concentrations reported are much higher than the maximum values observed in titanium silicates for which isomorphous substitution has been demonstrated. The possible presence of Ti02 particles has not been investigated. No indication of the properties of these materials as catalysts in reactions typical of titanium silicates has been provided. It is therefore very doubtful that real isomorphous substitution has been obtained (Skeels et al., 1989 Skeels, 1993). 

Most zeolites have an intrinsic ability to exchange cations [1], This exchange ability is a result of isomorphous substitution of a cation of trivalent (mostly Al) or lower charges for Si as a tetravalent framework cation. As a consequence of this substitution, a net negative charge develops on the framework of the zeolite, which is to be neutralized by cations present within the channels or cages that constitute the microporous part of the crystalline zeolite. These cations may be any of the metals, metal complexes or alkylammonium cations. If these cations are transition metals with redox properties they can act as active sites for oxidation reactions. 

The other way to introduce heterometals is their isomorphous substitution for Si in the framework, in a similar manner to the isomorphous substitution of Al. The heteroatoms should be tetrahedral (T) atoms. In hydrothermal synthesis, the type and amount of T atom, other than Si, that may be incorporated into the zeolite framework are restricted due to solubility and specific chemical behavior of the T-atom precursors in the synthesis mixture. Breck has reviewed the early literature where Ga, P and Ge ions were potentially incorporated into a few zeolite structures via a primary synthesis route [9]. However, until the late 1970s, exchangeable cations and other extraframework species had been the primary focus of researchers. 

The role of the template in the synthesis is not merely as a porogen on the contrary, it is also responsible for many key functions [5, 9, 10]. The template (typically cationic) balances the negative charge that characterizes zeolitic framework, due to the isomorphic substitution of Si(IV) by Al(III), prearranges the secondary building units (SBUs) toward the zeolitic framework, improves the gel synthesis conditions, especially the solubility of the silica precursors, and favors the thermodynamics of the reaction by stabilizing the porous zeolite framework. 

Corma, A., Navarro, M. T., Rey, F., Rius, J. and Valencia, S. Pure polymorph C of zeolite heta synthesized hy using framework isomorphous substitution as a structure-directing mechanism, Angew. Chem. Int. Ed., 2001, 40, 2277-2280. 

For the first time, a systematic uniform ab initio study of endohedral complexes of C60, Si60 and Ge60 with monoatomic cations (Li+, Na+, K+ and Rb+) and anions (F-, Cl% Br and P) was performed. The 3-21 G level (3-21+G for the anions) was used. This could be achieved by application of the multiplicative integral approximation [86], as implemented in the program BRABO [87]. The sequence studied for the cages bears a close resemblance with isomorphic substitution in zeolites modifying its catalytic activity via bridging hydroxyls. 

Zeolites and related materials prepared by isomorphous substitution of lattice atoms can also be considered as sohd solutions and yield specifically designed micro- and mesoporous catalysts. 

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