Investigation of the photocatalytic activity of TiO2--polyoxometalate systems.

The present study reports the investigation of polyoxometalate catalyzed electron transfer from the conduction band of photoexcited TiO2 to molecular oxygen. The oxidation of 1,2-dichlorobenzene (DCB) was used as an index reaction for evaluating the photocatalyst systems TiO2-PW12O40(3-), TiO2-SiW12O40,4- and TiO2-W10O32(4-) in oxygenated aqueous solution. Addition of these polyoxometalate (POM) anions to TiO2 suspensions resulted in significant rate enhancement for DCB oxidation. Photodegradation kinetics exhibited [POM] dependence, experiencing different maximum (k = 0.0318 min(-1), 0.0108 min(-1), and 0.0066 min(-1)) for each POM at different [POM] (0.1 mM PW12O40(3-), 0.07 mM SiW12O40,4- and 1 mM W10O32,4-respectively). The probability that the difference in the adsorption affinity of POMs on TiO2 surface could account for the observed ranking of photodegradation rates was ruled out by adsorption isotherm experiments that revealed similar binding constants for each POM (467 M(-1), 459 M(-1), and 417 M(-1) for PW12O40(3-), SiW12O40(4-), and W10O32(4-), respectively). DCB degradation over TiO2 with O2 or POM+O2 systems can be modeled by the Langmuir-Hinshelwood (saturation kinetics) model. The concentration-independent rate constants (kL-H) for TiO2-O2, TiO2-W10O32(4-), TiO2-SiW12O40(4-), and TiO2-PW12O40(3-) were 0.0818, 0.152, 0.421, and 0.638 min(-1), respectively. An analysis of deltaG for electron transfer from the conduction band of TiO2 to POMs in this study shows that the electron transfer takes place even when it is endothermic.