Characterization of Charge Separation in Visible Light-Sensitive TiO_2 by In-Situ ESR Spectroscopy

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In-situ ESR studies were curried out to characterize paramagnetic species as the trapped electrons and notes generated and explore their transfer processes under visible light illumination in partially reduced TiO_2 and naphthol-adsorbed TiO_2 at 77 K.1. For the partially reduced pure anatase and rutile particles, a broad singlet ESR spectra due to Ti^<3+> (trapped electron) decreased in intensity upon visible light illumination, and then restored to the initial intensity in the dark. For the TiO_2 (P25) particles, however, the signal restored up to 2.5-3 times greater than before. Through the analysis of the spectral line shape, it was found that the electrons are transferred from the anatase to the rutile particles by photoexcitation in reduced TiO_2(P25).2. For O_2^- formed on partially reduced TiO_2 nanoparticles, the O2 and the surface Ti^<3+> signals were increased by 2-3 times upon illumination with visible light and reduced to the initial one by annealing the sample to r.t. in … More the dark. Assuming a reversible electron transfer reaction between Ti^<4+>-O_2^<2->-Ti^<4+> and Ti^<4+>-O_2^- + Ti^<3+>, the photoresponse was kinetically analyzed in terms of the trapping site of the O_2^- species.3. For 1-naphthol-adsorbed TiO_2 in 2-propanol suspension, electrons were transferred from the charge-transfer complex of the naphthol bound to the TiO_2 surface to be trapped as inner Ti^<3+> under visible light illumination. The signal intensity of Ti^<3+> reflected the efficiency of the photosensitization, which depended significantly on the structure of adsorbed molecules and photon energies illuminated. The kinetic analysis of the photoresponse suggested that electron trapping as surface Ti^<3+> is involved in the interfacial charge transfer process.The study demonstrated that ESR spectroscopy is useful in evaluating the charge-separation efficiency in visible light-sensitive TiO_2 and presented interesting and fundamentally important results for deepening understandings of the charge transfer processes. Less