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Title: Strategic immobilisation of catalytic metal nanoparticles in metal-organic frameworks
Author: Anderson, Amanda E.
ISNI:       0000 0004 7234 4099
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 2017
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This thesis describes the synthesis, characterisation and catalytic testing of multifunctional immobilised metal nanoparticle in metal-organic framework (MOF) materials. Combining the activity of metal nanoparticles with the porosity and Lewis acidity of metal-organic frameworks provides a single catalytic material which can perform multi-step reactions. Strategies to immobilise the metal nanoparticles within the metal-organic frameworks have been investigated. Immobilisation has been achieved by applying three different methodologies. First, deposition of metal nanoparticle precursors within mesoporous MOFs is discussed. Chapter 3 shows the effectivity of the double solvents deposition technique to achieve dispersed and small nanoparticles of around 2.7 nm. The best system combined Pd nanoparticles with MIL-101(Cr). This system was further investigated in tandem reductive amination catalysis, discussed in Chapter 4, to investigate the activity and selectivity provided by these multifunctional catalysts. Another immobilisation technique was performed by coating Pd decorated SiO2 spheres with a MOF layer. Using this technique, MOF was grown cyclically in solution, providing tuneable shell thicknesses of MOF on the metal nanoparticle decorated oxide spheres. While the homogeneity of the MOF shell needs more optimisation, it was determined that the surface charge on the spheres played an important role in the growth of MOF in the desired location. Finally, the third immobilisation technique is the core-shell growth of MOF on colloidal metal nanoparticles. Polymer-capped metal nanoparticles with well-defined shapes were synthesised and characterised. From here, the optimisation of conditions for core-shell growth of UiO-66 and MIL-100(Sc) were investigated. Conditions which provided the desired core-shell morphology were found for both MOF types. These materials were then subsequently used in tandem reductive amination catalysis and a more straightforward styrene hydrogenation. It was shown that the metal nanoparticles remain active catalysts within either MOF shell and the MOF shell stabilises the metal nanoparticle and acts as a Lewis acid catalyst.
Supervisor: Wright, Paul Anthony ; Baddeley, Christopher J. Sponsor: Engineering and Physical Sciences Research Council (EPSRC) ; University of St Andrews
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Metal-organic frameworks ; Metal nanoparticles ; Catalysis ; Core-shell materials ; QD882.A6 ; Supramolecular organometallic chemistry ; Nanoparticles