The formation of H2O2 in oxygenated and deoxygenated aqueous solutions using immobilized TiO2 illuminated by black light (365 nm) was studied to verify the presence of hydroxyl radicals in TiO2 photocatalysis. In oxygen containing systems, formation of H2O2 proceeds through reduction of molecular oxygen by conduction band electrons or by recombination of hydroxyl radicals. In oxygen free solutions recombination of hydroxyl radicals constitutes the only pathway to H2O2 formation. Detection of H2O2 in absence of oxygen therefore serves as an indicator for hydroxyl radical formation. The H2O2 concentration was determined using the Ghormley triiodide method. It was found that a significant amount of H2O2 was produced in the deoxygenated aqueous solutions supporting the hypothesis of hydroxyl radical production in photocatalysis. To further elucidate the origin of the H2O2, experiments using the radical scavenger tris(hydroxymethyl)aminomethane (Tris) were conducted. The results showed that the H2O2 concentration increased in the oxygenated system as Tris protects the H2O2 from decomposition by hydroxyl radicals. In the deoxygenated system, no H2O2 could be detected due to hydroxyl radical scavenging by Tris, which prevents H2O2 formation. The results presented support the hypothesis that the hydroxyl radical is the primary oxidant in aqueous TiO2 photocatalysis.

In this work we present a new route to probe the efficiency of aqueous TiO

Nitrogen-modified TiO 2 thin films are obtained, for the first time, from aerosol-assisted (AA)CVD-prepared samples via a posttreatment method involving immersion in liquid ammonia to achieve nitrogen-modified TiO 2 and visible-light photo-activity. The resulting modified and unmodified TiO 2 films are characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution (HR)TEM, energy dispersive X-ray (EDX) spectroscopy, selected area electron diffraction (SAED), UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS). This shows that the films are $200 nm thick and contain anisotropic crystals of anatase TiO 2 . XPS shows that the nitrogen is successfully added to the surface of the film interstitially at 0.7 at.-%, but is only present to a film depth of 50 nm. The nitrogen doping causes a red shift in the absorption band and a band gap narrowing of $0.1 eV. The surface-bound nitrogen results from the post-treatment method of doping where the films are soaked in liquid ammonia before annealing. The photocatalytic efficiencies of the films under visible light (>385 nm) are evaluated by measuring formaldehyde formation from the probe molecule tris(hydroxymethyl)aminomethane (Tris). Hydrogen abstraction from Tris, obtained from, e.g., photocatalytically produced OH radicals, leads to formaldehyde formation which is then detected through a modified version of the Hantzsch reaction. The results show that the N-modified film possess remarkable photocatalytic properties with an apparent photochemical quantum yield of $8%.

The photocatalytic activity in aqueous solutions of TiO2 and Ag enhanced TiO2 sol-gel produced films was characterized using tris(hydroxymethyl)aminomethane (Tris) under black light (365 nm) and the observed differences in efficiency were further investigated by O2 adsorption studies using the same probe. Hydrogen abstracting species, such as hydroxyl radicals formed upon photocatalysis, are able to abstract hydrogen from Tris. This reaction leads to the formation of formaldehyde which was detected and quantified through a modified version of the Hantzsch reaction. It was found that the Ag enhanced TiO2 film increased the apparent quantum yield from 7% to 12%, partly as a result of a Schottky barrier formation at the metal-semiconductor interface and partly as the sensitizing effect of Ag nanoparticles extends the visible light absorption, which through electron transfer processes enable an efficient charge separation in the TiO2 by attracting acceptor species more efficiently than pure TiO2. The O2 adsorption studies in this paper showed that the Ag enhanced TiO2 film has a stronger adsorption affinity than pure TiO2 towards O2, which make the reduction of O2 more efficient with a subsequent enhanced electron-hole lifetime. It was also found that the Ag enhanced TiO2 film had a poorer adsorption affinity for Tris than the pure TiO2 film, which is a consequence of fewer available surface adsorption sites due to the Ag coverage at 64% which agrees well with the obtained adsorption equilibrium constants (K(LH(TiO2)) = 615 M(-1) and K(LH(Ag-TiO2)) = 320 M(-1)).

The impact of O

Four different TiO 2 films are formed on glass at 500°C by aerosol-assisted (AA)CVD, atmospheric pressure (AP)CVD, AACVD followed by APCVD, and APCVD followed by AACVD. The APCVD films are formed from reaction of TiCl 4 (g) whilst the AACVD films are made by decomposing Ti[OCH(CH 3 ) 2 ] 4 contained in an aerosol. The film composition is studied using X-ray photoelectron spectroscopy (XPS) to ascertain the purity of the films, and no Cl traces can be found on any of the surfaces. The use of different combinations of CVD gives rise to significant changes in microstructure and preferred orientations. X-ray diffraction (XRD) patterns and Raman spectroscopy (RS) confirm that TiO 2 in the anatase form is the dominant phase on all samples. All films show superhydrophilicity after 50 min of black-light irradiation. The photocatalytic efficiencies of the films are assessed qualitatively by an ink test based on Resazurin, and quantitatively studied by measuring formaldehyde formation from tris(hydroxymethyl)aminomethane (Tris). Both methods show that the AACVD film and the film seeded by APCVD are the most photocatalytically efficient ones, both having an apparent quantum yield (AQY) of around 4.2%, while the APCVD film and the film seeded by AACVD have an AQY of 0.8% and 1.5%, respectively. The changes in photocatalytic activity are explained in part by changes in film microstructure and the accessible surface area.

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