Abstract
The photocatalytic oxidation of dodecane and some of its derivatives (C 12H 26, 1 ; C 10H 21CHCH 2, 2 ; C 12H 25SH, 3 ; C 12H 25OH, 4 ; C 12H 25NH 2, 5 ; C 11H 23CHO, 6 ) has been studied in air-equilibrated aqueous TiO 2 suspensions. The distribution of the intermediate products has been monitored during the degradation. C 1–C 12 Monocarboxylic acids are formed in all cases, though in a low yield with substrates 1– 3 . With compounds 4– 6 , acids are formed in a higher yield (>45%), initially including a large proportion of dodecanoic acid and are accompanied by significant amounts of aldehydes and alcohols. Relative efficiencies vary over a factor of 300 from 1 to 5 and a lower limit for the quantum yield is 1.18 for the latter compound, suggesting participation of a chain process. The data suggest that alkylperoxyl radicals are formed through initial hydrogen abstraction on the photocatalyst surface and oxygen addition and their reactivity with the starting reagent determines the course of the reaction. Activated substrates such as compounds 5 and 6 , and to a lesser degree 4 , easily transfer a hydrogen from position 1.
Published Version
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