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Title: Exploiting isotopic enrichment for a solid-state NMR investigation of 'ADORable' zeolites and breathing metal-organic frameworks
Author: Bignami, Giulia Paola Maria
ISNI:       0000 0004 7234 3328
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 2018
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This thesis combines synthetic studies for isotopic enrichment with solid-state characterisation techniques to investigate two classes of microporous materials: zeolites and metal-organic frameworks (MOFs). These materials have a wide range of successful applications, from industrial catalysis to medicine, resulting in the increasing need for both a complete understanding of their unique structural features and synthetic methods to target new frameworks. Nuclear magnetic resonance (NMR) spectroscopy, thanks to its sensitivity to the local, atomic-scale, environment and its element specificity, is applied, in combination with powder X-ray diffraction (PXRD), electron microscopy, N2 adsorption and mass spectrometry, to the study of these materials. Oxygen atoms play a crucial role in the structure and chemistry of zeolites and MOFs, making 17O NMR an excellent tool for chemical and structural investigations. However, the low natural abundance of this isotope (0.037%) and the cost of 17O-enriched reactants require the development of atom-efficient synthetic processes for isotopic enrichment. In the first part of this work, the unconventional assembly-disassembly-organisation-reassembly (ADOR) method is applied to the Ge-doped UTL framework and optimised in reduced-volume conditions for economic enrichment to obtain 17O- and 29Si-enriched UTL-derived zeolites. In situ and ex situ solid-state characterisation studies show that isotopic enrichment not only enables a more detailed spectroscopic investigation, but also provides new insights into the mechanism of the ADOR process and its sensitivity to experimental conditions. In the second part of this work, dry gel conversion synthesis and a novel steaming procedure are studied as cost-effective 17O-enrichment pathways for Al, Ga and Sc mixed-metal terephthalate MOFs. 17O solid-state NMR spectroscopy, in combination with PXRD and electron microscopy, is employed to investigate cation disorder and 17O NMR spectra are shown to be sensitive to substitution of metal centers and conformational changes upon interaction with guest molecules.
Supervisor: Ashbrook, Sharon E. ; Morris, Russell Edward Sponsor: Engineering and Physical Sciences Research Council (EPSRC) ; European Research Council (ERC)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Microporous solids ; Solid-state NMR ; Isotopic enrichment ; TP159.M6B5 ; Molecular sieves ; Zeolites ; Porous materials ; Supramolecular organometallic chemistry ; Isotope separation ; Nuclear magnetic resonance spectroscopy