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Title: Application of titania photocatalysis for organic synthesis
Author: Grant, Neil
ISNI:       0000 0004 2726 1665
Awarding Body: University of Aberdeen
Current Institution: University of Aberdeen
Date of Award: 2012
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The addition of benzyltrimethylsilane to maleic anhydride mediated by TiO2 photocatalysis was initially investigated. The affect of changing the catalyst, the radical trap loading and the substitution of the benzyltrimethylsilane molecule was assessed. Cyclisation precursors based on benzyltrimethylsilane were prepared, but were found not to cyclise via TiO2 photocatalysis. A number of other systems were assessed for their ability to cyclise under TiO2 photocatalysis; tertiary amines, aminomethyltrimethylsilanes, phenoxymethyltrimethylsilanes and phenoxyacetic acids. Phenoxymethyltrimethylsilane and phenoxyacetic acid were found to add effectively to maleic anhydride under TiO2 photocatalysis conditions, however they were unreactive with regards to cyclisation. EPR spectroscopy has been employed to characterise further the reaction of benzylsilanes with maleic anhydride under TiO2 photocatalytic conditions. A number of EPR active species were observed; trapped holes and electrons, which reside within the TiO2 catalyst. In addition, methyl and benzyl radicals were observed and were found to originate from the oxidation of the benzylsilanes by trapped holes in the TiO2 catalyst. However, no radical species were observed from the maleic anhydride. These observations had the following consequences for the currently proposed reaction mechanism for the addition of benzyltrimethylsilane with maleic anhydride under TiO2 photocatalysis.  The observation of the benzyl radical definitely proved that the reactive intermediate was indeed the proposed benzyl radical  The absence of any maleic anhydride EPR active species cast doubt on the role of maleic anhydride as an electron trap. Moreover when maleic anhydride is removed from the reaction system, interstitial Ti3+ species is absent from the EPR spectra, indicating that maleic anhydride is in fact acting as a hole trap.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Electron paramagnetic resonance spectroscopy ; Free radicals (Chemistry) ; Photocatalysis