An instrumental evaluation of selected metal functionalised semiconductors in the facilitation of photo-organic transformations.
Underwood, Timothy Michael.
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Throughout this research study, various strategies to design, synthesise and test the photo-reactivity of attenuated wide band gap semiconductors in alcohol oxidation studies have been explored. An alizarin red-sensitised zinc oxide photocatalyst which was stabilised in a silver-sodium electrolyte effectively facilitated a broad aromatic and aliphatic alcohol oxidation table with reported conversions ranging from 10 to ≥ 99 %. A systematic characterisation of the alizarin red-sensitised zinc oxide investigated the photoelectronic migrations across the alizarin red–zinc oxide interface and detected the transfer of electrons from the highest occupied molecular orbital of alizarin to the defect site of zinc oxide at 507 nm. Further studies were directed towards the development of a novel titanium dioxide semiconductor that was activated by visible light. Three attempted strategies (pseudo perovskites [Cu3TiO5, Ni3TiO5, and Mn3TiO5], silver functionalised cadmium sulfide and a heterojunction between cadmium sulfide and titanium dioxide) explored the possibility of lowering the band gap potential of wide band gap semiconductors through metal ion functionalisation (Cu, Ni, Mn, and Ag) and heterojunction principles for the purpose of finding applications in mediating alcohol oxidations. Whilst the three strategies were unable to demonstrate viable photocatalytic properties, the instrumental insight obtained during the process identified a suitable three-component semiconductor system (Cu/Pd-N-TiO2). Cu/Pd-N-TiO2 was extensively characterised with an array of instrumental techniques, thus developing an in-depth understanding of the photophysical properties that governed the photo-oxidative transformation of a range of cyclic alcohols and in the remediation of two dyestuffs typically associated with environmental contamination.