One-step synthesis of black TiO_2-x microspheres by ultrasonic spray pyrolysis process and their visible-light-driven photocatalytic activities

Black TiO_2-x has recently emerged as one of the most promising visible-light-driven photocatalysts, but current synthesis routes that require a reduction step are not compatible with cost-effective mass production and a relatively large particle such as microspheres. Herein, we demonstrate a simple, fast, cost-effective and scalable one-step process based on an ultrasonic spray pyrolysis for the synthesis of black TiO_2-x microspheres. The process utilizes an oxygen-deficient environment during the pyrolysis of titanium precursors to directly introduce oxygen vacancies into synthesized TiO₂ products, and thus a reduction step is not required. Droplets of a titanium precursor solution were generated by ultrasound energy and dragged with continuous N₂ flow into a furnace for the decomposition of the precursor and crystallization to TiO₂ and through such a process spherical black TiO_2-x microspheres were obtained at 900 °C. The synthesized black TiO_2-x microsphere with trivalent titanium/oxygen vacancy clearly showed the variation of physicochemical properties compared with those of white TiO₂. In addition, the synthesized microspheres presented the superior photocatalytic activity for degradation of methylene blue under visible light irradiation. This work presents a new methodology for a simple one-step synthesis of black metal oxides microspheres with oxygen vacancies for visible-light-driven photocatalysts with a higher efficiency.