A multi-technique approach to characterise acidic surface properties of microporous catalysts


Type
Thesis
Change log
Authors
Bräuer, Pierre 
Abstract

Microporous catalysts belong to a class of materials that exhibit pore networks in the molecular dimension, that is, channel diameters less than 2 nm. The industrially most important microporous catalysts are zeolites, which are crystalline aluminosilicates and consist of interlinked alumina (AlO4) and silica (SiO4) tetrahedra forming pores and cavities of molecular dimensions. Zeolites can act as very strong solid acids and function as heterogeneous catalysts in various industrial processes used to obtain polyethylene terephthalate (PET) or polyvinyl chloride (PVC). They are crucial for products with a significant market demand such as plastics used in bottles, packaging materials and household consumable goods as well as for coatings of pharmaceutical pills and detergents. Recently, zeolites have been found to have increased applications in aqueous and biphasic reactions that use reactants derived from biomass to arrive at petrochemical products. Thus, surface acidity in zeolites is crucial to understand to tune parameters such as activity and selectivity of zeolite catalysts to optimize product distributions.

The objective of this dissertation was to validate the use of non-invasive nuclear magnetic resonance (NMR) techniques to characterise surface acidity in zeolites by benchmarking the NMR results to various more established zeolite characterisation techniques, such as Fourier transform infrared (FTIR) spectroscopy and temperature-programmed desorption (TPD). Furthermore, the use of the tapered element oscillating microbalance (TEOM) to characterise internal and external acidity in zeolites was explored. IR and TPD techniques were used to assess important acidity parameters such as type, number, location and strength of acid sites of ZSM-5 zeolites with varying silica-alumina ratio (SAR = SiO2/Al2O3). The use of NMR relaxation time analysis of pyridine adsorbed in ZSM-5 was then explored as a model system to study surface acidity in microporous materials. Correlation with pyridine TPD results suggested that NMR relaxation time analysis probes the effective strength of pyridine adsorption sites, which varies with SAR.

NMR relaxation time analysis was then further shown to be applicable to characterise non-acidic surface properties such as the hydrophilic and hydrophobic surface character. Lastly, the NMR techniques developed at high magnetic field strength (300 MHz) were transferred to a portable, low-cost benchtop low-field (43 MHz) magnet and shown to be applicable for base probe molecules other than pyridine, that is, ammonia (NH3) as well as zeolite framework types other than ZSM-5, that is, chabazite (CHA).

Description
Date
2018-03-28
Advisors
D'Agostino, Carmine
Keywords
zeolites, microporous materials, acidity, NMR relaxation
Qualification
Doctor of Philosophy (PhD)
Awarding Institution
University of Cambridge