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Oxidation of biomass-derived chemicals over redox active metalorganic frameworks
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Chamberlain, Thomas William (2021) Oxidation of biomass-derived chemicals over redox active metalorganic frameworks. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3766444
Abstract
The hydrothermal synthesis of a range of MOFs comprised of a variety of redox active metal ions was explored to produce a set of potentially redox active materials. These materials were fully characterised to determine their phase purities, thermal stabilities and the extent of incorporation of redox active metal ions. These MOFs would then be investigated for their catalytic activity towards the oxidation of 5-hydroxymethyl furfural to 2,5-furan dicarboxylic acid. Optimisation of the analysis and oxidation of HMF to FDCA was then carried out, where it was determined that 1H NMR was the most suitable analytical method for the analysis of the reaction products. A particular emphasis on the use of environmentally benign conditions throughout this project meant that water was used as the solvent for the majority of the reactions carried out in this project.
The catalytic activity of MIL-100(Fe) was then investigated, and it was found that the MOF, in combination with the co-catalyst TEMPO, was a highly efficient oxidation catalyst for the conversion of HMF to FDCA. Under optimal reaction conditions, MIL-100(Fe) was found to give an FDCA molar yield of 57% and an FFCA yields of 27% after 24 hours with a total molar selectivity of 84%. Comparisons with reference catalysts Fe2O3, FeCl3 and commercial Basolite F300 demonstrated a significant advantage associated with the Fe(III) incorporation into MIL- 100(Fe) over the more conventional materials. This work represents the first case of the use of a MOF for the complete oxidation of HMF to FDCA in water.
Finally, an attempt was made to probe a synthetic route to the substrate HMF via fructose over an isostructural yttrium version of a known dual acidic ytterbium MOF catalyst (Yb6-MOF) by photoluminescence. During the optimisation of the synthesis of this highly water stable yttriumbased MOF, Y6-MOF, a new phase, Y(BDC)(CH3COO) was isolated, and its structure solved. Although the use of photoluminescence to probe the conversion of glucose into HMF proved unsuccessful, it was instead discovered that by doping its structure with a precise ratio of Tb(III) and Eu(III) ions, its luminescent properties could be tuned. The MOF demonstrated impressive temperature dependent luminescent properties, which enabled it to act ratiometric luminescent thermometer over the 288 – 573 K temperature range.
| Item Type: | Thesis (PhD) | ||||
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| Subjects: | Q Science > QC Physics Q Science > QD Chemistry T Technology > TP Chemical technology |
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| Library of Congress Subject Headings (LCSH): | Organometallic compounds -- Synthesis, Metal ions, Oxidation, Oxidation-reduction reaction, Photoluminescence | ||||
| Official Date: | September 2021 | ||||
| Dates: |
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| Institution: | University of Warwick | ||||
| Theses Department: | School of Engineering | ||||
| Thesis Type: | PhD | ||||
| Publication Status: | Unpublished | ||||
| Supervisor(s)/Advisor: | Degirmenci, Volkan ; Walton, Richard I. | ||||
| Format of File: | |||||
| Extent: | viii, 222 leaves : illustrations, charts | ||||
| Language: | eng |
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