Active sites zeolite structures

Vanadium and sodium neutralize catalyst acid sites and can cause collapse of the zeolite structure. Figure 10-5 shows the deactivation of the catalyst activity as a function of vanadium concentration. Destruction of the zeolite by vanadium takes place in the regenerator where the combination of oxygen, steam, and high temperature forms vanadic acid according to the following equations ... 

Microporous catalysts are heterogeneous catalysts used in catalytic converters and for many other specialized applications, because of their very large surface areas and reaction specificity. Zeolites, for example, are microporous aluminosilicates (see Section 14.19) with three-dimensional structures riddled with hexagonal channels connected by tunnels (Fig. 13.38). The enclosed nature of the active sites in zeolites gives them a special advantage over other heterogeneous catalysts, because an intermediate can be held in place inside the channels until the products form. Moreover, the channels allow products to grow only to a particular size. 

Figure 4.1. Representation of the pore structure of HZSM5, one of the most important zeolites industrially. The vertical cylinders represent one pore network, and the other cylinders an interconnecting network. The narrow pores, and their almost complete uniformity, means that only some molecules can enter. Others are excluded, and cannot react at the active sites, which are found within the structure. Thus, the reactivity of a molecule is determined by its shape and size, rather than by its electronic properties. Such a situation is almost unique, with the only exception being enzymes, where molecules must fit into the enzyme active site in order to react.

Zeolites are used in various applications such as household detergents, desiccants and as catalysts. In the mid-1960s, Rabo and coworkers at Union Carbide and Plank and coworkers at Mobil demonstrated that faujasitic zeolites were very interesting solid acid catalysts. Since then, a wealth of zeolite-catalyzed reactions of hydrocarbons has been discovered. Eor fundamental catalysis they offer the advantage that the crystal structure is known, and that the catalytically active sites are thus well defined. The fact that zeolites posses well-defined pore systems in which the catalytically active sites are embedded in a defined way gives them some similarity to enzymes. 

When supported complexes are the catalysts, two types of ionic solid were used zeolites and clays. The structures of these solids (microporous and lamellar respectively) help to improve the stability of the complex catalyst under the reaction conditions by preventing the catalytic species from undergoing dimerization or aggregation, both phenomena which are known to be deactivating. In some cases, the pore walls can tune the selectivity of the reaction by steric effects. The strong similarities of zeolites with the protein portion of natural enzymes was emphasized by Herron.20 The protein protects the active site from side reactions, sieves the substrate molecules, and provides a stereochemically demanding void. Metal complexes have been encapsulated in zeolites, successfully mimicking metalloenzymes for oxidation reactions. Two methods of synthesis of such encapsulated/intercalated complexes have been tested, as follows. 

Recrystallization procedure applied to the amorphous aluminosilicates of different chemical composition resulted in the formation of the dispersed zeolitic domains of the FAU and BEA structure in porous matrices. The structural transformation into the composite material was proved with TEM, XRD and 27Al and 29Si MAS NMR spectroscopies. The IR data revealed that strong Bronsted acid centers were main active sites generated in the composite materials, irrespectively of the Al content. 

Despite several decades of studies devoted to the characterization of Fe-ZSM-5 zeolite materials, the nature of the active sites in N20 direct decomposition (Fe species nuclearity, coordination, etc.) is still a matter of debate [1], The difficulty in understanding the Fe-ZSM-5 reactivity justifies a quantum chemical approach. Apart from mononuclear models which have been extensively investigated [2-5], there are very few results on binuclear iron sites in Fe-ZSM-5 [6-8], These DFT studies are essentially devoted to the investigation of oxygen-bridged binuclear iron structures [Fe-0-Fe]2+, while [FeII(p-0)(p-0H)FeII]+ di-iron core species have been proposed to be the active species from spectroscopic results [9]. We thus performed DFT based calculations to study the reactivity of these species exchanged in ZSM-5 zeolite and considered the whole nitrous oxide catalytic decomposition cycle [10],... 

Zeolite molecular sieves are widely used as solid acid catalysts or catalyst components in areas ranging from petroleum refining to the synthesis of intermediates and fine chemicals (112,113). An important reason for their widespread use is the flexibility they oflFer regarding the tailoring of the concentration and nature of catalytically active sites and their immediate environments. We note that discrimination between chemical and structural aspects works well at a conceptual level, but one faces quite severe limitations as soon as one tries to separate the contributions of the two effects. The complexity arises because the chemical properties of a particular molecular sieve are connected with its framework density. 

The separation of a reactant system (solute) from its environment with the consequent concept of solvent or surrounding medium effect on the electronic properties of a given subsystem of interest as general as the quantum separability theorem can be. With its intrinsic limitations, the approach applies to the description of specific reacting subsystems in their particular active sites as they can be found in condensed phase and in media including the rather specific environments provided by enzymes, catalytic antibodies, zeolites, clusters or the less structured ones found in non-aqueous and mixed solvents [1,3,6,8,11,12,14-30],... 

Following the discovery of TS-1 [125], a titanium-substituted MFl, the use of zeolitic materials for oxidation increased significantly. The presence of the Ti atom in the framework of a zeolite structure provides a site-isolated Ti center, a situation not possible with other Ti-containing materials while also allowing shape-selective oxidations. The combination of the two effects gives highly active and selective oxidation reactions [126]. 

Boronat, M., Virrruela, M., and Corma, A. (2004) Reaction intermediates in acid catalysis by zeolites prediction of the relative tendency to form alkoxides or carbocations as a function of hydrocarbon nature and active site structure. 

Zeolite catalysts play a vital role in modern industrial catalysis. The varied acidity and microporosity properties of this class of inorganic oxides allow them to be applied to a wide variety of commercially important industrial processes. The acid sites of zeolites and other acidic molecular sieves are easier to manipulate than those of other solid acid catalysts by controlling material properties, such as the framework Si/Al ratio or level of cation exchange. The uniform pore size of the crystalline framework provides a consistent environment that improves the selectivity of the acid-catalyzed transformations that form C-C bonds. The zeoHte structure can also inhibit the formation of heavy coke molecules (such as medium-pore MFl in the Cyclar process or MTG process) or the desorption of undesired large by-products (such as small-pore SAPO-34 in MTO). While faujasite, morden-ite, beta and MFl remain the most widely used zeolite structures for industrial applications, the past decade has seen new structures, such as SAPO-34 and MWW, provide improved performance in specific applications. It is clear that the continued search for more active, selective and stable catalysts for industrially important chemical reactions will include the synthesis and application of new zeolite materials. 

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