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Title: The photocatalytic degradation of phenolic compounds
Author: Clarke, Jill
ISNI:       0000 0001 2445 964X
Awarding Body: Open University
Current Institution: Open University
Date of Award: 1998
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Semiconductor photocatalysis degrades phenolic pollutants to carbon dioxide and water, but the mechanisms of this potentially attractive method of environmental remediation remain unclear. This study aimed to elucidate the primary molecular events by HPLC analysis of the initial products of degradation in water or aqueous acetonitrile. The position of substituents relative to the hydroxyl group were found to influence the reaction rate and also primary oxidation steps, and hence the intermediate profile. 2,6- Dialkylated phenols reacted fastest and showed high conversion to dehydrodimeric products as a prelude to degradation. In contrast, 3,5-dialkylated phenols and 4-tertbutylphenol reacted more slowly and appeared to degrade directly to small polar compounds with little accumulation of primary carbocyclic intermediates. The rate of photocatalytic degradation of two isomeric dibromohydroxybenzonitriles was also influenced by substitution pattern. 3,5-Dibromo-2-hydroxybenzonitrile, however, is itself photolabile in daylight giving 3-bromo-2,5-dihydroxybenzonitrile in aqueous solution. The analogous reaction does not occur for 3,5-dibromo-4-hydroxybenzonitrile, the difference in behaviour being attributed to differences in the electronic spectra of the two compounds. The mechanism of photocatalysis appears to be influenced by the orientation of the substrate on the catalyst surface. For the alkyl phenols, particularly those with tert-butyl substitution, minimisation of disturbance to the polar network of the solvent directs the more hydrophobic parts of the molecule towards the oxidising surface of the catalyst. In addition, this effect encourages clustering of molecules with the subsequent formation of aggregated products. While part of the behaviour observed may be attributable to the presence of acetonitrile in the solvent, the hydrophobic profile of a substrate undergoing heterogeneous photocatalytic oxidation in water would seem to be a significant determinant of the molecular pathway selected in the first phase of its degradation.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
Keywords: Remediation; Semiconductors; Titanium oxide