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Stable metal organic frameworks for the catalytic destruction of chemical warfare agents
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dc.contributor.advisor | Morris, Russell Edward | |
dc.contributor.author | Elliott, Caroline | |
dc.coverage.spatial | 235 | en_US |
dc.date.accessioned | 2023-06-30T15:28:54Z | |
dc.date.available | 2023-06-30T15:28:54Z | |
dc.date.issued | 2023-11-29 | |
dc.identifier.uri | https://hdl.handle.net/10023/27864 | |
dc.description.abstract | The work described within this Thesis has focused on the preparation and characterisation of metal-organic frameworks (MOFs) as catalysts for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP). Mixed-metal MOFs were explored for this application using a combination of zirconium and hafnium in known MOFs in order to investigate the role of Lewis-acidity on catalysis. A series of mixed-metal MOFs were prepared and successfully catalysed the hydrolysis of DMNP. For UiO-66 and NU-1000 the highest rates were seen for the Zr 100% samples. For MOF-808 the most successful catalyst was found to be the Zr 33% Hf 66% sample. Further investigations compared properties of each sample and concluded that a change in Lewis-acidity plays a role in the catalytic activity, despite differences in material characteristics. Mixed-linker MOFs were also investigated through the addition of di-topic linkers to a MOF-808 synthesis. For each sample, ca. 10\% of a chosen di-topic linker, as a proportion of linker present, was incorporated into the MOF-808 structure. Further investigations using the 5-amino isophthalic acid di-topic linker found up to 25% of 5-amino isophthalic acid could be incorporated into MOF-808. All samples successfully hydrolysed DMNP, with the 20% 5-amino isophthalic acid MOF-808 sample giving the highest rate and out-performing the parent MOF-808 sample. Investigations into preparing MOF-composite materials were also carried out. This focused on incorporating MOF-808 into the materials PET, cotton, silk and nylon, using a range of synthesis methods. Loading estimates were calculated through q-NMR measurements. All materials saw MOF-808 successfully deposited on the surface, with the exception of one sample. All materials tested as catalysts for the hydrolysis of DMNP outperformed the blank samples. MOF-808 had therefore retained catalytic properties within the composite material. The hydrothermal synthesis method using PET displayed the highest initial rate for all composite materials prepared. | en_US |
dc.description.sponsorship | "I would also like to thank the EPSRC, University of St Andrews and CRITICAT Centre for Doctoral Training for financial support (grant number EP/L016419/1) and Capital for Great Technologies (grant number EP/L017008/1)."--Acknowledgements | en |
dc.language.iso | en | en_US |
dc.subject | MOF | en_US |
dc.subject | Chemical warfare agents | en_US |
dc.subject | Zirconium | en_US |
dc.subject | Hafnium | en_US |
dc.subject | Composite materials | en_US |
dc.subject.lcc | QD411.E66 | |
dc.subject.lcsh | Metal organic frameworks | en |
dc.subject.lcsh | Chemical agents (Munitions) | en |
dc.subject.lcsh | Zirconium | en |
dc.subject.lcsh | Hafnium | en |
dc.subject.lcsh | Composite materials | en |
dc.title | Stable metal organic frameworks for the catalytic destruction of chemical warfare agents | en_US |
dc.type | Thesis | en_US |
dc.contributor.sponsor | Engineering and Physical Sciences Research Council (EPSRC). Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) | en_US |
dc.contributor.sponsor | University of St Andrews | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
dc.identifier.doi | https://doi.org/10.17630/sta/527 | |
dc.identifier.grantnumber | EP/L016419/1 | en_US |
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