Role of Surface/Interfacial Cu2+ Sites in the Photocatalytic Activity of Coupled CuO−TiO2 Nanocomposites

Coupled CuO−TiO2 nanocomposite photocatalysts were prepared by a deposition precipitation method and were characterized with a variety of techniques. Electron paramagnetic resonance (EPR) spectroscopy was employed to study the local structures of surface/interfacial Cu2+ sites using Cu2+ as a sensitive paramagnetic probe. The addition of bulk CuO to TiO2 led to decreased photocatalytic efficiency in the degradation of methylene blue. However, doping with a very small amount of CuO (0.1 wt % copper loading) significantly enhanced the photocatalytic activity of TiO2. EPR study of the TiO2 surface revealed the presence of both highly dispersed CuO clusters and substitutional Cu2+ sites (Ti−O−Cu linkages) at 0.1 wt % copper loading. The data suggest that the Ti−O−Cu linkages contributed to the improved photooxidative activity of the 0.1% CuO−TiO2 nanocomposite. In contrast, at higher loadings the bulk form of CuO created charge recombination centers lowering the photoactivity of the composites.