Visible light-driven photocatalytic degradation of the organic pollutant methylene blue with hybrid palladium–fluorine-doped titanium oxide nanoparticles

The synthesis of mesoporous aggregates of titanium oxide nanoparticles (F0) is described using a very cheap and simple synthetic protocol. This consists of the reaction of titanium tetraisopropoxide and a solution of HNO3 in water (pH 2.0) and subsequent filtration. In addition, fluorine-doped titanium oxides (F1, F2, F5 and F10) were synthesized using the same method, adding increasing amounts of NaF to the reaction mixture (avoiding the use of expensive reagents such as NH4F or trifluoroacetic acid). The resulting materials were calcined at different temperatures (500, 600 and 650 °C) giving particles sized between 10 and 20 nm. Furthermore, a hybrid F-doped TiO2 with supported palladium nanoparticles of ca. 20 nm (F5-500-Pd1) was synthesized by grafting an organometallic palladium(II) salt namely [Pd(cod)Cl2] (cod = 1,5-cyclooctadiene). Photocatalytic studies of the degradation of methylene blue (MB) were carried out under UV light using all the synthesized material (non-doped an F-doped TiO2), observing that the increase in the quantity of fluorine has a positive effect on the photocatalytic activity. F5-500 is apparently the material which has the most convenient structural properties (in terms of surface area and anatase/rutile ratio) and thus a higher photocatalytic activity. The hybrid material F-doped TiO2–Pd nanoparticles (F5-500-Pd1) has a lower band gap value than F5-500, and thus photocatalytic degradation of MB under LED visible light was achieved using F5-500-Pd1 as photocatalyst.