Zeolites polarity

Reliable mechanistic conclusions require high intrazeolite yields that account for the majority of the substrate mass balance. This can be a challenge because of the small-scale reactions often conducted for mechanistic studies. In addition, rapid removal of the products from the zeolite, and/or low conversions to decrease residence time, is occasionally necessary because of the sensitivity of the reaction products to the zeolite environment.44,45 Intrazeolite products are generally recovered by extractive techniques from either the intact zeolite, or from a mixture formed after mild digestion of the zeolite. Polar solvents such as tetrahydrofuran or acetonitrile coupled with a continuous extraction technique is in particular an effective means to remove polar products with an affinity for the interior of the zeolite.44 Zeolite digestion with mineral acids, in order to liberate the products, must be conducted with care in order to prevent acid catalyzed product decomposition or reaction.46,47... 

Zeolite polarity and reaction rate The competition between sulfolane, PA and product molecules for the adsorption on the active protonic sites is sufficient enough to explain the differences in reaction orders and catalyst stability and selectivity between PA transformation in sulfolane and in dodecane. However, the competition for the occupancy of the zeolite micropores plays a significant role as well. This was demonstrated by studying a related reaction the transformation of an equimolar mixture of PA with phenol in sulfolane solvent on a series of H-BEA samples with different framework Si/Al ratios (from 15 to 90).[49] According to the largely accepted next nearest neighbour model,[50,51] the protonic sites of these zeolites should not differ by their acid strength, as furthermore confirmed by the... 

Competition between reactant, solvent and product molecules for adsorption within the zeolite micropores is demonstrated directly (adsorption experiments) and indirectly (effect of the framework Si/Al ratio on the activity, kinetic studies) to occur during Fine Chemical synthesis over molecular sieve catalysts. This competition, which is specific for molecular sieves (because of confinement effects within their micropores), adds up to the competition which exists over any catalyst for the chemisorption of reactant, solvent and product molecules on the active sites. Both types of competition could affect significantly the activity, stability and selectivity of the zeolite catalysts. Although the relative contributions of these two types of competition cannot be estimated, the large change in the activity of the acidic sites (TOF) with the zeolite polarity seems to indicate that the competition for adsorption within the zeolite micropores often plays the major role. 

Silica and Alumina Gels, Zeolites Polar vapors water, alcohols, phenols, chlorophenols, glycols, aliphatic and aromatic amines... 

Guest molecules may interact favorably with each other upon absorption within a zeolite. Whatever interactions a pure substance may have amongst its atoms or molecules, may be carried into the void space of a zeolite. Polar molecules may continue to orient favorably, hydrogen-bonding molecules may continue that interaction, and formal chemical bonds can reform within the zeolite. Van der Waals liquids may continue to be that upon sorption by a zeolite. 

Enhanced activity of zeolites with respect to alumina silica gel type of catalysts was ascribed to the enhanced mobility of the protons in the crystalline zeolite bringing about increased acid strength.(73) Thus,though individual catalytic sites may be equivalent, their ensembles of different size would have different catalytic activity.(75) Furthermore C-13 nuclear magnetic resonance of adsorbed molecules showed that strong electric forces present in the regular pores of crystalline zeolites polarize and activate adsorbed molecules (155). 

Adsorbents Table 16-3 classifies common adsorbents by structure type and water adsorption characteristics. Structured adsorbents take advantage of their crystalline structure (zeolites and sllicalite) and/or their molecular sieving properties. The hydrophobic (nonpolar surface) or hydrophihc (polar surface) character may vary depending on the competing adsorbate. A large number of zeolites have been identified, and these include both synthetic and naturally occurring (e.g., mordenite and chabazite) varieties. 

For a polar surface and molecules with permanent dipole moments, attraction is strong, as for water adsorption on a hydrophilic adsorbent. Similarly, for a polar surface, a molecule with a permanent quadrupole moment vidll be attracted more strongly than a similar molecule with a weaker moment for example, nitrogen is adsorbed more strongly than oxygen on zeolites (Sherman and Yon, gen. refs.). 

The diffusion, location and interactions of guests in zeolite frameworks has been studied by in-situ Raman spectroscopy and Raman microscopy. For example, the location and orientation of crown ethers used as templates in the synthesis of faujasite polymorphs has been studied in the framework they helped to form [4.297]. Polarized Raman spectra of p-nitroaniline molecules adsorbed in the channels of AIPO4-5 molecular sieves revealed their physical state and orientation - molecules within the channels formed either a phase of head-to-tail chains similar to that in the solid crystalline substance, with a characteristic 0J3 band at 1282 cm , or a second phase, which is characterized by a similarly strong band around 1295 cm . This second phase consisted of weakly interacting molecules in a pseudo-quinonoid state similar to that of molten p-nitroaniline [4.298]. 

Molecular sieves (dehydrated zeolite) purify petroleum products with their strong affinity for polar compounds such as water, carbon dioxide, hydrogen sulfide, and mercaptans. The petroleum product is passed through the sieve until the impurity is sufficiently removed after which the sieve may be regenerated by heating to 400 - bOO F. 

Zeolites are naturally occurring hydrous aluminum-sodium silicates in porous granule form. They are capable of exchanging their sodium base for calcium or magnesium and of expelling these alkaline earth metals for sodium by treatment with salt. Thus, they are a type of ion-exchange media. (Some zeolites act as molecular sieves by adsorption of water and polar compounds.)... 

The results indicate that the zeolite can selectively extract specific compounds from the reaction medium, due to the different affinity towards each of them. This makes possible to develop reactant concentrations inside pores which are different from the bulk ones. This property is a function of the zeolite hydrophobic characteristics, which are affected by the Si/Al ratio. The best zeolite is that one which does not interact too strongly neither with more polar molecules, so to allow activation of formaldehyde to proceed faster, nor with the least polar ones. The intermediate Si/Al ratio in H-mordenites is able to develop the optimal concentration ratio between reactants inside the pores, and to reach the highest yield to vanillols. 

Faujasites are highly hydrophilic materials. In the transformation of apolar compounds such as hydrocarbons, all other molecules have higher polarity, so the rate of transformation is seriously decreased because the more polar products adsorb preferentially on the zeolite. This was a serious problem in the oxidation... 

Ellison EH, Moodley D, Hime J (2006) Fluorescence study of arene probe microenvironment in the intraparticle void volume of zeolites interfaced with bathing polar solvents. J Phys Chem B 110 4772 1781... 

For cationic zeolites Richardson (79) has demonstrated that the radical concentration is a function of the electron affinity of the exchangeable cation and the ionization potential of the hydrocarbon, provided the size of the molecule does not prevent entrance into the zeolite. In a study made on mixed cationic zeolites, such as MgCuY, Richardson used the ability of zeolites to form radicals as a measure of the polarizing effect of one metal cation upon another. He subsequently developed a theory for the catalytic activity of these materials based upon this polarizing ability of various cations. It should be pointed out that infrared and ESR evidence indicate that this same polarizing ability is effective in hydrolyzing water to form acidic sites in cationic zeolites (80, 81). 

Fontes tt al. [224,225 addressed the acid—base effects of the zeolites on enzymes in nonaqueous media by looking at how these materials affected the catalytic activity of cross-linked subtilisin microcrystals in supercritical fluids (C02, ethane) and in polar and nonpolar organic solvents (acetonitrile, hexane) at controlled water activity (aw). They were interested in how immobilization of subtilisin on zeolite could affected its ionization state and hence their catalytic performances. Transesterification activity of substilisin supported on NaA zeolite is improved up to 10-fold and 100-fold when performed under low aw values in supercritical-C02 and supercritical-ethane respectively. The increase is also observed when increasing the amount of zeolite due not only to a dehydrating effect but also to a cation exchange process between the surface proton of the enzyme and the sodium ions of the zeolite. The resulting basic form of the enzyme enhances the catalytic activity. In organic solvent the activity was even more enhanced than in sc-hexane, 10-fold and 20-fold for acetonitrile and hexane, respectively, probably due to a difference in the solubility of the acid byproduct. 

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