Advances in Chemical Engineering: Photocatalytic by Hugo I. De Lasa

By Hugo I. De Lasa

The cross-fertilization of physico-chemical and mathematical principles has a protracted ancient culture. This quantity of Advances in Chemical Engineering is nearly thoroughly devoted to a convention on 'Mathematics in Chemical Kinetics and Engineering' (MaCKiE-2007), which used to be held in Houston in February 2007, bringing jointly approximately forty mathematicians, chemists, and chemical engineers from 10 nations to debate the appliance and improvement of mathematical instruments of their respective fields.

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1985). All of them are positive enough to be reduced by TiO2 conduction band electrons (Figure 3). , 2001, 2004): À CrðVIÞ þ ecb ! CrðVÞ ð20Þ À ! CrðIVÞ CrðVÞ þ ecb ð21Þ À ! CrðIIIÞ CrðIVÞ þ ecb ð22Þ Treatment of Heavy Metals and Metalloids in Water by Heterogeneous Photocatalysis 47 These assumptions were validated, at least for the initial one-electron process (20), by EPR experiments in which Cr(V) species were detected. While the fate of Cr(V) and Cr(IV) is not clear, it is hypothesized that they are probably reduced by conduction band electrons or can suffer disproportionation to other species.

O2 þ 4Hþ ð13Þ The photogenerated holes or HO• radicals can reoxidize also the species to the original one, causing a nonproductive short-circuiting of the overall process: • nþ MðnÀ1Þþ þ hþ vb =HO ! , 1993a). The process can be improved even more if a strong reducing species is formed Treatment of Heavy Metals and Metalloids in Water by Heterogeneous Photocatalysis R• 43 Rox (b) Mn+ cb ecb– M(n–1)+ (b) (a) Mn+ M(n–1)+ hν HR Mn+ (c) vb HO– R• M(n+1)+ (c) HO• hvb+ Figure 3 Schematic diagram for the photocatalytic transformation of metal ions on TiO2.

If O2 competes with Cr(VI) for conduction band electrons, a faster Cr(VI) reduction should have been obtained over Pt/TiO2, as platinum reduces the overpotential for oxygen reduction. Experimental results suggest that electron transfer to metallic ion from the conduction band or from Pt is rapid and there is no oxygen mediation requirement. 3. , 2008). The behavior of Cr(VI) contrasts strongly with that of other metal ions such as Hg(II) (see section 4), whose reduction is greatly inhibited by dissolved oxygen.

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