Zeolites acidic/basic properties

The most commonly employed crystalline materials for liquid adsorptive separations are zeolite-based structured materials. Depending on the specific components and their structural framework, crystalline materials can be zeoUtes (silica, alumina), silicalite (silica) or AlPO-based molecular sieves (alumina, phosphoms oxide). Faujasites (X, Y) and other zeolites (A, ZSM-5, beta, mordenite, etc.) are the most popular materials. This is due to their narrow pore size distribution and the ability to tune or adjust their physicochemical properties, particularly their acidic-basic properties, by the ion exchange of cations, changing the Si02/Al203 ratio and varying the water content. These techniques are described and discussed in Chapter 2. By adjusting the properties almost an infinite number of zeolite materials and desorbent combinations can be studied. 

The acidic/basic properties of zeolites can be changed by introdnction of B, In, Ga elements into the crystal framework. For example, a coincorporation of alnminnm and boron in the zeolite lattice has revealed weak acidity for boron-associated sites [246] in boron-snbstitnted ZSM5 and ZSMll zeolites. Ammonia adsorption microcalorimetry gave initial heats of adsorption of abont 65 kJ/mol for H-B-ZSMll and showed that B-substituted pentasils have only very weak acidity [247]. Calcination at 800°C increased the heats of NH3 adsorption to about 170 kJ/mol by creation of strong Lewis acid sites as it can be seen in Figure 13.13. The lack of strong Brpnsted acid sites in H-B-ZSMll was confirmed by poor catalytic activity in methanol conversion and in toluene alkylation with methanol. 

Zeolite could selectively adsorb A -nitrosamines in the solution of methylene chloride or water, and the equilibrium data were fitted to Freundlich-type isotherms. Textural and acid-basic properties of zeolite determined their adsorption capacity. The extraordinary adsorption properties of NaA zeolite for iV-nitrosamines is inferred that the adsorbates inert the channel with the group -N=N-0. Larger amount of A-nitrosamines was adsorbed on ZSM-5 zeolite in water instead in methylene chloride, due to the hydrophobicity of the zeolite. Application of zeolite to remove A-nitrosamines from beer seems successful. Up to 100% of the worst carcinogenic compounds could thus be removed with 1.4 g/L of zeolite which was proven to be better adsorbent than silica or alumina. On Na 3 zeolite and MCM-41 mesoporous material A-nitrosodimethylamine decomposed above 573 K and the liberated NOx could be detected even at 773 K during the TPSR process, indicating the strong adsorption of A-nitrosamines on molecular sieves that makes zeolite become the functional materials for environmental protection. 

Other types of mesoporous materials have also attracted attention. For example, HMS (hexagonal mesoporous silicate) materials may be prepared with different A1 contents, similarly to common zeolites. HMS samples with an Si/Al ratio = 2.5, either in the H form or after partial exchange with Li" or Na+ cations, exhibit much less marked acidic/basic properties than comparable zeoHtes, though their chemical composition is close to that of Y zeolites [288]. Differential heats of CO2 adsorption at low coverage of 32 and 26 kJ mol were measured on the li and Na-exchanged samples respectively. This feature is ascribed to the amorphous nature of the walls, to be contrasted with the crystalline structure of zeoUtes [288]. 

The purpose of this work was to increase the A3 selectivity at low conversion through a catalyst modification. Previous studies of phenol alkylation with methanol (the analogue reaction) over oxides and zeolites showed that the reaction is sensitive to acidic and basic properties of the catalysts [3-5]. It is the aim of this study to understand the dependence of catalyst structure and acidity on activity and selectivity in gas phase methylation of catechol. Different cations such as Li, K, Mg, Ca, B, incorporated into y-Al203 can markedly modify the polarisation of the lattice and consequently influence the acidic and basic properties of the surface [5-8] which control the mechanism of this reaction. 

Alumina is an amphoteric catalyst, which can difficult to characterize via chemical and physic methods. The transformation of cyclopentanol/cyclohexanone mixture allows us to estimate at the same time the acid-base properties of aluminas. From this transformation, it was shown that aluminas can be classified into two families only basic aluminas, such as theta, which were more basic than MgO, and acido-basic aluminas, eta, gamma and delta, which possess an acidic character less pronounced than dealuminated HMOR zeolite... 

Acidic properties of zeolitic materials have widely been investigated in the past fifteen years ( 1), particularly for Y-type zeolites. The presence of strong acid sites, as it is usually the case for acid zeolites, results in the presence of only weak basic sites, if any. Therefore, up to now, majority of the studies has dealt with the characterization of acid+rather than basic properties. The acid sites (Bronsted s H, Lewis Al) and basic sites (0, OH ) may be characterized directly by using physical... 

The foundation of equilibrium-selective adsorption is based on differences in the equilibrium selectivity of the various adsorbates with the adsorbent While all the adsorbates have access to the adsorbent sites, the specific adsorbate is selectively adsorbed based on differences in the adsorbate-adsorbent interaction. This in turn results in higher adsorbent selectivity for one component than the others. One important parameter that affects the equilibrium-selective adsorption mechanism is the interaction between the acidic sites of the zeolite and basic sites of the adsorbate. Specific physical properties of zeolites, such as framework structure, choice of exchanged metal cations, Si02/Al203 ratio and water content can be... 

Owing to the possibility of tuning (1) their acidic and basic properties, (2) their surface hydrophilicity, and (3) their adsorption and shape-selectivity properties, catalytic activity of zeolites was investigated in the production of HMF from carbohydrates. Whatever the hexose used as starting material, acidic pillared montmorillonites and faujasite were poorly selective towards HMF, yielding levu-linic and formic acids as the main products [81-83]. 

Microcrystalline solids such as zeolites and zeolite like structures have shown the utility of those properties in the domain of acid catalysis. However, little is known on their possibilities as base catalysts. It has been shown [ref. 1,2] that zeolites have basic sites which are able to catalyze reactions needing weak and medium basic strengths. Moreover, a correlation between the basicity and the Sanderson s average electronegativity Df the framework has been observed [ref. 3], Then, their activity as base catalysts can be modified by changing the countercation [ref. 4], the framework Si/Al ratio, or by introducing atoms other than Si and Al in the framework [ref. 5],... 

Since the last review by Venuto in 1968,[1] there has been a continuous interest in the application of microporous and mesoporous materials as catalysts in the synthesis of bulk and fine chemicals.[211 Indeed, their acidic and basic properties can be combined with their structural properties in order to take advantage of their adsorption and shape selectivity properties, the latter being an advantageous feature of zeolites compared with other heterogeneous catalysts. Another important aspect... 

The unique properties of zeolites and other micro- or mesoporous solids that may favour their application to fine chemical synthesis are (1) the compatibility between the size and shape of their channels or cavities with the size of the reactants and/or products (generally referred to as molecular shape selectivity) that may direct the reaction away from the thermodynamically favoured route (2) the occurrence of confinement effects increasing the concentration of reactants near the catalytic sites and (3) the ability to tune their catalytic properties (acidic, basic, or other) via various treatments as described in this Volume. 

At the basis of the application of zeolites in fine chemicals reactions is the rich variety of catalytic functions with which zeolites can be endowed. Bronsted acidity, Lewis acidity and metallic functions are well known from classical bifunctional chemistry but for specific reactions, unusual sites, e.g. Lewis acid Ti4+ centres, have been introduced into zeolites. Moreover, zeolites can acquire more or less weakly basic properties metal complexes can be entrapped in zeolite pores or cavities, and enantioselective reactions have been performed by decorating the zeolite surface with chiral modifiers. 

The influence of catalyst supports is being widely studied at present. Metal complexes or clusters are applied un supports like silica, alumina or zeolites [42, I30[. Tliesc supports influence the molecular weight distribution, not only by their acidic or basic properties but also by their ability to stabilize metal dispersions and by their geometric properties. 

Catalytic properties of crystalline aluminosilicates generally are corre- lated with acidic species in the zeolite framework. Many reports deal with the nature and location of this acidity, which has been extensively investigated with infrared spectroscopy before and after reaction of the zeolite with basic species. 

The chemical selectivity obtained in the alkylation of aromatic molecules over zeolitic catalysts critically depends upon their acid base properties. While xylenes are the primary products in the methylation of toluene over acidic zeolites like HZSM5 [e.g. 1,2,3], ethylbenzene and styrene are formed over basic zeolites such as Rb-X and Cs-X [e g. 4,5,6]. Previous reports suggested the surface chemistry of chemisorbed methanol to be the most decisive parameter to determine the selectivity [7,8]. Recent experiments on toluene methylation to xylenes indicated, however, that various bimolecular precursors to the transition state in the rate determining step exist and may be important for the catalytic properties of zeolites [9,10],... 

A number of methods are used for studying the sorption of basic probe molecules on zeolites to learn more about zeolite acidity. A common disadvantage of all the examinations is that adsorbed basic probe increases the electron density on the solid and, thereby, change the acidic properties of the sites examined. From this aspect it seems advantageous to probe the acid sites with a weak base, e. g., with a hydrocarbon. It was shown that adsorption of alkanes is localized to the strong Brdnsted acid sites of H-zeolites [1, 2]. However, recent results suggest that usually the diffusion in the micropores controls the rate of hydrocarbon transport [3-5]. Obviously, the probe suitable for the batch FR examination of the sites has to be non-reactive and the sorption dynamics must control the rate of mass transport. The present work shows that alkanes can not be used because, due to their weak interaction with the H-zeolites, the diffusion is the slowest step of their transport. In contrast, acetylene was found suitable to probe the zeolitic acid sites. The results are discussed in comparison with those obtained using ammonia as probe. Moreover, it is demonstrated that fundamental information can be obtained about the alkane diffusivity in H-zeolites... 

The reaction of phenol alkylation with methanol over oxides and zeolites to produce anisol and cresols presents some of the features of the reaction under investigation. Studies of phenol alkylation revealed that the reaction was sensitive to the acid-base properties of the catalyst [5-13]. The catalytic activity increased with acidity, but the selectivity towards O- or C-methylated products did not follow a simple correlation with observed acid-base properties. According to [7,12,16] the catalysts with basic sites favour C-methylation. Other authors [6,11] recently reported that an increase in catalyst acidity promote C-methylation. Therefore, a variance in the results concerning acidity and catalytic properties exists in the literature. 

This paper presents a comprehensive overview of heterogeneously catalysed MPVO reactions. It includes the recent application of zeolites as new recycleable solid catalysts for the MPVO reaction. The activity of these catalysts is related to their Lewis acid and/or basic properties. Some remarkable examples of shape-selective conversions resulting in high stereoselectivities have recently been found by our group. 

Heterogeneous catalysts which are active for the catalysis of the MPVO reactions include amorphous metal oxides and zeolites. Their activity is related to their surface basicity or Lewis acidity. Zeolites are only recently being developed as catalysts in the MPVO reactions. Their potential is related to the possibility of shape-selectivity as illustrated by an example showing absolute stereoselectivity as a result of restricted transition-state selectivity. In case of alkali or alkaline earth exchanged zeolites with a high aluminium content (X-type) the catalytic activity is most likely related to basic properties. For zeolite BEA (Si/Al=12), however, the dynamic character of those aluminium atoms which are only partially connected to the framework appear to play a role in the catalytic activity. Similarly, the Lewis acid character of the titanium atoms in aluminium free [Ti]-BEA explains its activity in the MPVO reactions. 

---