N3-Dye-Induced Visible Laser Anatase-to-Rutile Phase Transition on Mesoporous TiO(2) Films

Titanium dioxide has been extensively used in photocatalysis and dye-sensitized solar cells, where control of the anatase-to-rutile phase transformation may allow the realization of more efficient devices exploiting the synergic effects at anatase/rutile interfaces. Thus, a systematic study showing the proof of concept of a dye-induced morphological transition and an anatase-to-rutile transition based on visible laser (532 nm) and nano/micro patterning of mesoporous anatase (Degussa P25 TiO(2)) films is described for the first time using a confocal Raman microscope. At low laser intensities, only the bleaching of the adsorbed N3 dye was observed. However, high enough temperatures to promote melting/densification processes and create a deep hole at the focus and an extensive phase transformation in the surrounding material were achieved using Is laser pulses of 25-41 mW/cm(2), in resonance with the MLCT band. The dye was shown to play a key role, being responsible for the absorption and efficient conversion of the laser light into heat. As a matter of fact, the dye is photothermally decomposed to amorphous carbon or to gaseous species (CO(x), NO(x), and H(2)O) under a N(2) or O(2) atmosphere, respectively.

Unravelling the Chemical Morphology of a Mesoporous Titanium Dioxide Interface by Confocal Raman Microscopy: New Clues for Improving the Efficiency of Dye Solar Cells and Photocatalysts

The presence of anatase and rutile domains on nanocrystalline films of P25 TiO(2), as well as the distinct coordination modes of carboxylates on those phases, were revealed by confocal Raman microscopy, a technique that showed to be suitable for imaging the chemical morphology down to submicrometric size.

Evidences for charge-transfer complex formation in the benzene adsorption on sulfated TiO2-a resonance Raman spectroscopy investigation

Benzene adsorbed on highly acidic sulfated TiO2 (S-TiO2) shows an intriguing resonance Raman (RR) effect, with excitation in the blue-violet region. There are very interesting spectral features: the preferential enhancement of the e(2g) mode (1595 cm(-1)) in relation to the a(1g) mode (ring-breathing mode at 995 cm(-1)) and the appearance of bands at 1565 and 1514 cm(-1). The band at 1565 cm(-1) is probably one of the components of the e(2g) split band, originally a doubly degenerate mode (8a, 8b) in neat benzene, and the band at 1514 cm(-1) is assigned to the 19a mode, an inactive mode in neat benzene. These facts indicate a lowering of symmetry in adsorbed benzene, which may be caused by a strong interaction between S-TiO2 and the benzene molecule with formation of a benzene to Ti (IV) charge transfer (CT) complex or by the formation of a benzene radical cation species. However, the RR spectra of the adsorbed benzene cannot be assigned to the benzene radical cation because the observed wavenumber of the ring-breathing mode does not have the value expected for this species. Moreover, it was found by ESR measurements that the amount of radicals was very low, and so it was concluded that a CT complex is the species that originates the RR spectra. The most favorable intensification of the band at 1595 cm(-1) in the RR spectra of benzene/S-TiO2 at higher excitation energy corroborates this hypothesis, as an absorption band in this energy range, assigned to a CT transition, is observed. Copyright (C) 2008 John Wiley & Sons, Ltd.

XPS characterization of sensitized n-TiO2 thin films for dye-sensitized solar cell applications

TiO2 thin films, employed in dye-sensitized solar cells, were prepared by the sol-gel method or directly by Degussa P25 oxide and their surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The effect of adsorption of the cis-[Ru(dcbH(2))(2)(NCS)(2)] dye, N3, on the surface of films was investigated. From XPS spectra taken before and after argon-ion sputtering procedure, the surface composition of inner and outer layers of sensitized films was obtained and a preferential etching of Ru peak in relation to the Ti and N ones was identified. The photoelectrochemical parameters were also evaluated and rationalized in terms of the morphological characteristics of the films. (c) 2007 Elsevier B.V. All rights reserved.

Heterogeneous photocatalytic degradation of acid dyes in aqueous TiO2 suspensions: Kinetics and toxicity

This work assesses the photocatalytic (TiO2/UV) degradation of a simulated acid dye bath (Yellow 3, Red 51, Blue 74, and auxiliary chemicals). Color and phytotoxicity removal were monitored by spectrophotometry and lettuce (Lactuca sativa) seeds as the test organism, respectively. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 240 minutes of irradiation, it was achieved 96% and 78% of color removal with photocatalysis and photolysis, respectively. 37% of mineralization occurred with photocatalysis only. The dye bath was rendered completely non-toxic after 60 minutes of photocatalytic treatment; the same result was only achieved with photolysis after 90 minutes. A kinetic model composed of two first-order in series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 0.062 min(-1) and the second k(2) = 0.0043 min(-1), approximately two times greater than the photolytic ones.