Photocatalytic Activity of Cu–TiO2 Nanopowder Under UVA and Sunlight Illumination: Influence of Composition and Calcination Temperature on Charge Transfer

Cu–TiO2 nanoparticles of a broad range of compositions with 0, 0.002, 0.005, 0.02, 0.05, 0.2, 0.5, 1.0, 2.0, 3.0, 5.0, 7.0 and 10.0 mol% Cu were synthesized via the sol–gel method using copper (II) acetate and titanium tetraisopropoxide (TTIP) precursors at a low hydrolysis ratio of H = 1.25, which favours homogeneous TiO2 nucleation and Cu dispersion in the host matrix at nanoscale. The precipitated materials were dried at 80 °C and calcined at 450, 500, and 550 °C to form crystalline nanopowders, whose photocatalytic activity was evaluated on the decomposition of a representative pollutant, methylene blue (MB), in aqueous solutions under UVA and sunlight illuminations. The compositions with small Cu content of ~0.05 mol% showed the highest activity. A gain of activity over pure titania of 4 times after calcination at 450 °C, 2.5 times at 500 °C and 20% at 550 °C was measured under UVA illumination. Even higher gain of activity observed under sunlight illumination might be due to an extension of action spectrum to the visible range due to intra-gap defect states produced by Cu2+ insertion. The time-resolved microwave conductivity (TRMC) measurements of the photoinduced charges relaxation suggest that both excessive calcination temperature and Cu content decrease the activity due to Cu-defects clustering. Modelling relates the activity to the photoinduced electron-hole pair separation; the optimal Cu content is explained by accessibility of the recombination centre by a conduction band (CB) electron. Accordingly, an increase in calcination temperature resulted in a longer pathlength of CB electron.