Simultaneous enhancement of natural sunlight- and artificial UV-driven photocatalytic activity of a mechanically activated ZnO/SnO2 composite

Mechanical milling of commercial ZnO and SnO2 was used to produce a ZnO/SnO2 composite with a high density of surface defects; in particular, zinc interstitials (Zni) and oxygen vacancies (VO). To determine the impact of surface defects on photocatalytic activity, the relative concentration ratio of bulk defects to surface defects was modified by annealing at 400 and 700 °C. The possible application of the ZnO/SnO2 composite as a natural sunlight and UV-light driven photocatalyst was revealed via de-colorization of methylene blue. In both cases the ZnO/SnO2 composite exhibited enhanced photocatalytic activity as compared to the pristine ZnO. In order to investigate the origin of the enhancement, the pristine metal oxides and composites were characterized using a variety of techniques, including X-ray diffraction (XRD), Raman and Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), laser diffraction particle size analysis, Brunauer–Emmett–Teller, UV-Vis diffuse reflectance and photoluminescence spectroscopy. High-resolution transmission electron microscopy (HRTEM) and elemental mapping analyses were used to reveal the presence of SnO2 nanocrystallites on the surface of larger ZnO particles. The enhanced photocatalytic activity of the composite can be attributed to the synergetic effect of the surface defects and the ZnO/SnO2 heterojunction particles, which facilitated charge separation, thereby hindering the recombination of photogenerated carriers. This study draws attention to mechanical activation as an inexpensive and environmentally friendly technique for the large-scale production of the composite with an enhanced photocatalytic activity under illumination of either UV or sunlight.