Photocatalytic degradation of methylene blue by TiO2–Cu thin films: Theoretical and experimental study

▶ The depth and surface Cu dopant concentration can be modulated by thermal treatment of TiO2. ▶ H2O2 can be degraded by TiO2 electron/hole pair as well as by Cu metallic and ionic species, trough of a Like-Fenton mechanism. ▶ The colorant degradation occurs due successive hydoxylations. In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO2 films were studied. TiO2 films of about 200nm thickness were deposited on glass substrates on which a thin Cu layer (5nm) was deposited. The films were annealed during 1s to 100°C and 400°C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO2, Cu2O and Cu0 phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet–visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations.