Visible-light-driven CQDs/TiO2 photocatalytic simultaneous removal of Cr(VI) and organics: Cooperative reaction, kinetics and mechanism

Abstract

CQDs/TiO₂ was synthesized with a coprecipitation method and characterized by XRD, SEM, TEM/HRTEM, BET, XPS, UV-Vis DRS and I-t curve technologies. UV-Vis DRS displayed that absorption spectrum of CQDs/TiO₂ enlarged to visible light zone, suggesting that CQDs/TiO₂ can be irradiated by visible light. I-t curve showed that photocurrent of CQDs/TiO₂ was higher than that of bare TiO₂, revealing that the doping of CQDs accelerated the transfer of photoelectrons and restrained the recombination of photoinduced carriers. Simultaneous removal of Cr(VI) and organics with CQDs/TiO₂ photocatalytic reaction was investigated and factors were optimized, and almost all Cr(VI) and organics were removed under the optimum conditions. Experimental results displayed that there was a distinct cooperation removal effect between Cr(VI) and organics in CQDs/TiO₂ photocatalytic reaction. XPS analysis proved that Cr(VI) was reduced to Cr(III) in situ on CQDs/TiO₂ surface. There were e^-, h⁺,·OH and ·O₂^- active species which were detected with DMPO in ESR test during CQDs/TiO₂ photocatalytic reaction, and scavenger experiment proved that e^- and h⁺ were the substantial reactants for Cr(VI) and organics, respectively. The pathway of photocatalytic simultaneous removal of Cr(VI) and organics underwent four steps: adsorption of Cr(VI) and organics on CQDs/TiO₂ surface; production of photo electrons and holes in visible light; reduction of Cr(VI) and oxidation of organics; desorption of Cr(III) and intermediates. Photocatalytic reaction kinetics of Cr(VI) and organics were both confirmed to pseudo first-order reaction. Life span and small scale real application tests both demonstrated that CQDs/TiO₂ had a potential application to wastewater containing Cr(VI) and organics.

Keywords: CQDs/TiO(2); Cr(VI); Photocatalytic removal; TiO(2); Visible light.