Photocatalytic thin films containing TiO2:N nanopowders obtained by the layer-by-layer self-assembling method

Abstract

In this work, TiO2–N powders were synthesized by high-energy ball milling, using commercial titanium dioxide (TiO2) in the anatase phase and urea to introduce nitrogen into TiO2 in order to enhance their photocatalytic properties in the visible spectral region. Several samples were prepared by milling a mixture of TiO2–urea during 2, 4, 8, 12 and 24 h and characterized by spectroscopic and analytical techniques. X-ray diffraction (XRD) results showed the coexistence of anatase and high-pressure srilankite TiO2 crystalline phases in the samples. Scanning electron microscopy (SEM) revealed that the grain size of the powder samples decreases to 200 nm at 24 h milling time. UV–Vis diffuse reflectance spectroscopic data showed a clear red-shift in the onset of light absorption from 387 to 469 nm as consequence of nitrogen doping in the samples. The photocatalytic activity of the TiO2–N samples was evaluated by methylene blue degradation under visible light irradiation. It was found that TiO2–N samples had higher photocatalytic activity than undoped TiO2 samples, which could be assigned to the effect of introducing N atoms and XPS results confirm it. Using polyethylenimine (PEI), transparent thin films of TiO2–N nanoparticles were prepared by layer-by-layer self assembly method. UV–visible spectrophotometry was employed in a quantitative manner to monitor the adsorbed mass of TiO2 and PEI after each dip cycle. The adsorption of both TiO2 and PEI showed a saturation dip time of 15 min.