Fabrication and fluorescence study of sensitizing dye TiO2 films

Fluorescence spectra of the sensitizing dye/TiO2 bilayer films were studied. Charge-transfer complexes were formed in the above bilayer.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

A rapid method of assessing the photocatalytic activity of thin TiO2 films using an ink based on the redox dye 2,6-dichloroindophenol

An indicator ink based on the redox dye 2,6-dichloroindophenol ( DCIP) is described, which allows the rapid assessment of the activity of thin, commercial photocatalytic films, such as Activ. The ink works via a photoreductive mechanism, DCIP being reduced to dihydro-DCIP within ca. 7.5 minutes exposure to UVA irradiation of moderate intensity ( ca. 4.8mW cm(-2)). The kinetics of photoreduction are found to be independent of the level of dye present in the ink formulation, but are highly sensitive to the level of glycerol. This latter observation may be associated with a solvatochromic effect, whereby the microenvironment in which the dye finds itself and, as a consequence, its reactivity is altered significantly by small changes in the glycerol content. The kinetics of photoreduction also appear linearly dependent on the UVA light intensity with an observed quantum efficiency of ca. 1.8 x 10(-3). Copyright (C) 2008.

Photocatalytic oxidation of deposited sulfur and gaseous sulfur dioxide by TiO2 films

Thick (4 mu m) films of anatase titania are used to photocatalyze the removal of deposited films of amorphous sulfur, similar to 2.8 mu m, thick and under moderate illumination conditions (I = 5.6 mW cm(-2)) on the open bench the process is complete within similar to 8 or 18 h using UVC or UVA light, respectively. Using UVA light, 96% of the product of the photocatalytic removal of the film of sulfur is sulfur dioxide, SO2. The photonic efficiency of this process is similar to 0.16%, which is much higher (> 15 times) than that of the removal of soot by the same films, under similar experimental conditions. In contrast to the open bench work, in a closed system the photocatalytic activity of a titania film toward the removal of sulfur decreased with repeated use, due to the accumulation of sulfuric acid on its surface generated by the subsequent photocatalytic oxidation of the initial product, SO2. The H2SO4-inactivated films are regenerated by soaking in water. The problems of using titania films to remove SO2 from a gaseous environment are discussed briefly.

Photochemical reduction of oxygen adsorbed to nanocrystalline TiO2 films: A transient absorption and oxygen scavenging study of different TiO2 preparations

Transient absorption spectroscopy (TAS) has been used to study the interfacial electron-transfer reaction between photogenerated electrons in nanocrystalline titanium dioxide (TiO2) films and molecular oxygen. TiO2 films from three different starting materials (TiO2 anatase colloidal paste and commercial anatase/rutile powders Degussa TiO2 P25 and VP TiO2 P90) have been investigated in the presence of ethanol as a hole scavenger. Separate investigations on the photocatalytic oxygen consumption by the films have also been performed with an oxygen membrane polarographic detector. Results show that a correlation exists between the electron dynamics of oxygen consumption observed by TAS and the rate of oxygen consumption through the photocatalytic process. The highest activity and the fastest oxygen reduction dynamics were observed with films fabricated from anatase TiO2 colloidal paste. The use of TAS as a tool for the prediction of the photocatalytic activities of the materials is discussed. TAS studies indicate that the rate of reduction of molecular oxygen is limited by interfacial electron-transfer kinetics rather than by the electron trapping/detrapping dynamics within the TiO2 particles.

Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO₂ films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO₂ film to UV light. All such films exhibit the optical characteristics (λ_max ≅ 390 nm) of small (<20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (>40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapordeposited films. The Ag/TiO₂ films exhibit a lower residual standard deviation (∼25%) compared with Ag vapor-deposited films (∼45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (<7%) by spinning the film during the SERS measurement. The Ag/TiO₂ films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO₂ films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO₂, is briefly discussed. 

Anodic stripping voltammetry with photochemical preconcentration at nanocrystalline TiO2 films: Detection of Ag+ and Hg2+

Nanocrystalline TiO2 deposited on conducting glass plates is shown to be an excellent material for preconcentration of silver and mercury, via photochemical reaction, prior to their detection by anodic stripping voltammetry (ASV). During the first stage of growth in the photoreduction of silver or mercury, 3D nuclei are formed on the TiO2 film. As the deposition proceeds micrometer size agglomerates grow on the surface. The conical morphology of the silver nuclei grown on a (110) rutile single crystal in the initial stages of growth suggests that there is a preferential deposition of silver at the centre of the growing nuclei. When the nuclei size reach a critical value (ca. 400 nm diameter, 40 nm height) the morphology changes to a globular shape without any preferential site for deposition on the surface of the silver nucleus. It was observed that micromolar concentrations of silver or mercury can be detected by anodic stripping voltammetry and relatively large amounts of these metals (micrometer scale nuclei) can be loaded on the nanocrystalline TiO2 film surface. The latter opens the possibility of analytical applications of nanocrystalline TiO2 electrodes for the selective detection of silver or mercury via photochemical anodic stripping voltammetry.

Quantum yield measurements for the photocatalytic oxidation of Acid Orange 7 (AO7) and reduction of 2,6-dichloroindophenol (DCIP) on transparent TiO2 films of various thickness

This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

Rapid, simple method for determining the porosity of mesoporous TiO2 films using a quartz crystal microbalance (QCM)

Two different mesoporous films of TiO2 were coated onto a QCM disc and fired at 450o C for 30 min. The first film was derived from a sol-gel paste that was popular in the early days of dye-sensitised solar cell, i.e. dssc, research, a TiO2(sg) film. The other was a commercial colloidal paste used to make examples of the current dssc cell; a TiO2(ds) film. A QCM was used to determine the mass of the TiO2 film deposited on each disc and the increase in the mass of the film when immersed in water/glycerol solutions with wt% values spanning the range 0-70%. The results of this work reveal that with both TiO2 mesoporous films the solution fills the film's pores and acts as a rigid mass, thereby allowing the porosity of each film to be calculated as: 59.1% and 71.6% for the TiO2(sg) and TiO2(ds) films, respectively. These results, coupled with surface area data, allowed the pore radii of the two films to be calculated as: 9.6 and 17.8 nm, respectively. This method is then simplified further, to just a few frequency measurements in water and only air to reveal the same porosity values. The value of the latter ‘one point’ method for making porosity measurements is discussed briefly.

Structural and Electronic Effects of Incorporating Mn in TiO2 Films Grown by Sputtering: Anatase versus Rutile

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

Evaluation of pure and Ag-doped TiO2 films in the photocatalytic activity of phenol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)