Photocatalytic degradation of azo dyes by organic-capped anatase TiO2 nanocrystals immobilized onto substrates

The UV-induced photocatalytic degradation of two azo dyes, Methyl Red and Methyl Orange, has been carried out in aqueous media in the presence of oleic acid (OLEA)- and tri-n-octylphosphine oxide (TOPO)-capped anatase TiO2 nanocrystal powders (mean particle size: 6 nm) deposited onto a quartz substrate. The progress of photodegradation was followed by combining UV-vis absorption measurements with HPLC-MS analysis. The abatement efficiency for the two organic compounds was compared with that obtained with commercial TiO2 P25 Degussa by evaluating a few significant variables, such as the dye chemical structure, pH of the solution, and catalyst surface status. Identification of several by-products by HPLC-MS analysis has allowed to propose a reasonable degradation pathway for both target molecules. Significantly, although all titania catalysts were effective in removing both parent dyes and their related derivatives, the degradation rate by the OLEA-capped TiO2 nanocrystals was double as that obtained with both its TOPO-capped analogous and TiO2 P25 Degussa. It is suggested that efficient catalysis strictly depends on microscopic mechanisms that occur at the catalyst surface, basically involving specific dye adsorption and local density of terminal -OH moieties. (C) 2004 Elsevier B.V. All rights reserved