Oxygen species, photocatalytic oxidation

Most photocatalytic studies conducted at low aromatic concentrations report no detectable concentrations of gas-phase intermediates [12,17,18]. Traces of intermediates may be present in the gas phase, but at levels below the detection limits of the analytical instruments employed in these studies. There is evidence, however, for either reaction intermediates or reaction by-products on the catalyst surface, even at these low concentrations. Catalyst discoloration, typically a yellowish or brownish color, is often reported following the photocatalytic oxidation of aromatic contaminants at low to moderate gas-phase concentrations [3,4,7,17,52]. These intermediates or reaction by-products may be largely trapped on the catalyst surface by the higher affinity of oxygenated species, like alcohols and aldehydes, for TiO, surfaces when compared to the aromatic parent compounds. 

Simultaneous measurements of the photocatalytic activity A and of the photoconductance a in a specially designed cell yield information on the participation of the oxygen species in the oxidation process. For instance, in the case of isobutane (IS) oxidation over TiC>2, the following relations were found (39) ... 

A varying and much more complex mechanistic situation exists in heterogeneous photocatalysis (Fig. 5-13). With respect to the transient oxygen species, comparable overall oxidation reactions are usually observed, but the set of primary reactive oxygen species is slightly different. It is commonly assumed, that superoxide radical anions and hydroxyl radicals are the primary species formed after photogeneration of the electron-hole pair of a semiconductor catalyst in the presence of water and air (Serpone, 1996). In the presence of ozone, ozonide radical anions or are formed by fast electron transfer reaction of superoxide radical anions with O3 molecules. The combination Ti02-03-UV/VIS is called photocatalytic ozonation (Kopf et al., 2000). For example, it was applied for the decomposition of tri-chloroethene in the gas phase (Shen and Kub, 2002). 

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