Characterization of zeolite structure and fluorocarbon reactivity using solid state NMR and x-ray powder diffraction

The research presented in this thesis involves a combination of techniques used to study the structure and interactions zeolites adsorbed with fluorocarbons. This research is specifically aimed at understanding the processes of adsorption, binding, and reactivity of fluorocarbons on cation exchanged faujasite type zeolites. The solid state ion exchange process has also been studied since it is one way to obtain materials with higher exchange levels, which has been shown to effect adsorption and catalytic activity.; To improve the understanding of the adsorption and separation processes a time resolved in-situ synchrotron x-ray powder diffraction study has been undertaken. Since faujasite type zeolites have been found to be effective in separating mixtures of HFC-134 (CF₂HCF₂H) and HFC-134a (CFH₂CF₃) isomers, the adsorption of these fluorocarbons on NaY have been studied. It has been shown that both the extent of loading and the kinetics of the sorption process in molecular sieves can be followed using this technique.; A model for the binding of hydrochlorofluorocarbon (HCFC) 124a (CF ₂HCF₂Cl) adsorbed on NaX at 100K has been determined using a combination x-ray and neutron powder diffraction and solid state NMR. Using Rietveld refinement of the diffraction data, the HCFC molecule was found localized in the zeolite cavities bound on either end by sodium cations in the SII and SIII′ positions. The model is consistent with hydrogen bonding between the proton of the HCFC and the framework oxygen. The NMR results further confirm the model and are consistent with Na-F binding and HCFC-framework interactions.; Solid-state MAS NMR, synchrotron X-ray powder diffraction and a mass spectrometer and gas chromatograph catalysis system have been used to study the reactivity of HCFC-124a (CF₂HCF₂Cl) on NaX, Zn 2+-exchanged NaX (ZnX) and Rb+-exchanged NaX (RbX). We have chosen to study HCFC-124a (CF₂HCF₂Cl) since HCFC-124a can undergo both dehydrofluorination and dehydrochlorination reactions. The preference between these two reactions should be related to the relative importance of the interactions with the basic oxygen atoms and the cations. RbX is considered a basic zeolite while ZnX should have more acidic character, which should be reflected in differences in product distribution. The positions of the exchanged cations and the residual sodium cations of both exchanged zeolites have been located and the products formed during reaction have been identified.; To investigate possible methods to achieve high levels of cation substitution, NH₄Y has been ion exchanged with solid Rb₂CO₃ to form RbY. This process has been followed with x-ray powder diffraction, mass spectrometry and NMR. It has been shown that exchange begins on grinding and no rubidium oxide or new carbonate phases were observed to form during the exchange. The positions of the cations of the final exchanged RbY product have been located with Rietveld analysis. It has also been shown that 1H and 87Rb MAS NMR is very sensitive to the level of hydration of the zeolite and has been used to follow the solid state exchange process.