Photocatalytic removal of hexavalent chromium by newly designed and highly reductive TiO2 nanocrystals

Hexavalent chromium Cr(VI), a highly toxic oxyanion, widely occurs in drinking water supplies. This study designed and synthesized a new type of highly reductive TiO2 nanocrystals for photochemical Cr(VI) removal, via the thermal hydrolysis of TiCl4 in the presence of diethylene glycol (DEG). Surface analyses and hydroxyl radical measurements suggested that DEG was chemically bonded on TiO2 surface that resulted in an internal hole-scavenging effect and a high electron-releasing capacity, making it advantageous to conventional TiO2 materials. Upon UV irradiation, the synthesized TiO2 photocatalyst exhibited fast Cr(VI) reduction kinetics in diverse water chemical conditions. Fast elimination of Cr(VI) was achieved on a time scale of seconds in drinking water matrices. The removal of Cr(VI) by reductive TiO2 exhibited a three-stage kinetic behavior: an initial fast-reaction phase, a lag phase resulting from surface precipitation of Cr(OH)3(s), and a final reaction phase due to surface regeneration from oxidation-reduction induced ripening process. The lag phase disappeared in acidic conditions that prevented the formation of Cr(OH)3(s). The catalyst exhibited extremely high electron-releasing capacity that can be reused for multiple cycles of Cr(VI) removal in drinking water treatment. [Display omitted] •A novel reductive TiO2 was synthesized by thermal hydrolysis of TiCl4 in diethylene glycol.•Chemically-bonded diethylene glycol promoted strong internal hole-scavenging effect.•Synthesized TiO2 showed fast Cr(VI) reduction kinetics in diverse water conditions.•High electron-releasing capacity was shown for multiple cycles of Cr(VI) removal.