Reinvestigation of the photocatalytic reaction mechanism for Pt-complex-modified TiO2 under visible light irradiation by means of ESR spectroscopy and chemiluminescence photometry.

A plausible reaction mechanism for a visible light photocatalyst of TiO(2) modified with platinum(IV) chloride (PtCl) was proposed on the basis of the measurements with electron spin resonance (ESR) spectroscopy and chemiluminescence photometry. Under visible light (λ > 500 nm) irradiation, the deposited Pt(IV) chloride is charge-separated into Pt(3+) and Cl radical by the excitation of the ligand-to-metal charge transfer. The Pt(3+) gives an electron to the conduction band of TiO(2), which has Pt(3+) return to Pt(4+). The electron in the conduction band reduces the oxygen molecule into O(2)(-). The presence of Pt(3+) and O(2)(-) has been elucidated in the present study. Moreover, valence band holes of TiO(2) were detected by ESR spectroscopy under visible light irradiation. Therefore, besides being used to oxidize organic compounds, the photogenerated Cl radicals likely receive electrons from the TiO(2) valence band by visible light excitation, producing the valence band holes. Because the valence band holes have a stronger oxidation power than Cl radicals, the excitation of valence band electrons to Cl radicals would be the origin of the high photocatalytic activity of the PtCl-modified TiO(2) under visible light irradiation.