Natural Diatomite Supported Zirconium-Doped TiO₂ with Tailoring Band Structure for Enhanced Visible-Light...

The development of economically applicable, highly efficient and low cost photocatalytic materials has always been a challenge. In this work, we report a zirconium doped TiO2/diatomite (ZrTD) composite with enhanced visible light-induced photocatalytic activity. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, UV-VIS diffused reflectance spectroscopy, high-performance liquid chromatography-mass spectrometry, photoluminescence and X-ray photoelectron spectroscopy, respectively. The optimal doping ratio of zirconium into TiO2 was obtained at 3% (3%ZrTD composite), and the degradation rate constant of which tetracycline (TC) is up to around 8.65 times higher that of zirconium doped TiO2. In addition, zirconium doping introduces the impurity levels of Zr 3d and oxygen vacancies into the lattice of TiO2, resulting in broadening the light absorption range, reducing the band gap, and improving the separation efficiency of photogenerated electron-hole pairs, thus endowing with visible light photocatalytic properties. Moreover, both the photogenerated holes (h+) and superoxide (•O2-) radicals are responsible for the degradation process of TC, and a possible degradation pathway and the corresponding intermediate products of TC by ZrTD composite are also proposed in detail.