Photocatalytic degradation of tetrabromobisphenol A by Z-scheme WO3/ZnIn2S4 heterojunction: Efficiency, mechanism and toxicity evaluation

Abstract

Occurrence of brominated flame retardants especially tetrabromobisphenol A (TBBPA) in water bodies poses a serious threat to aquatic ecosystems. Heterogeneous photocatalysis is a versatile technology that can efficiently degrade organic contaminants. However, existing studies on photocatalytic degradation of TBBPA are all achieved under intense light irradiation and high initial concentrations of TBBPA, which are far from real environmental conditions and not conducive to practical application. In this study, series of Z-scheme heterojunctions of WO3/ZnIn2S4 photocatalysts were prepared and used for the high-efficiency photocatalytic degradation of TBBPA at lower light irradiation intensity (100 W) and lower TBBPA concentration (5.4 mg/L). Among them, WO3/ZnIn2S4-3 (molar ratio of 1:3) exhibited the highest photocatalytic activity due to the formation of Z-Scheme heterojunction which effectively facilitated the separation of photogenerated charges and endowed WO3/ZnIn2S4-3 higher redox ability. Thus, under light illumination, 91.6% degradation of TBBPA was achieved at an initial pH of 8.0 within 150 min, with a pseudo-first-order rate constant of 0.01572 min−1. Electron spin resonance spectroscopy and radical scavenger experiments confirmed that ·O2− radicals were the primary reactive oxygen species driving the TBBPA degradation. By applying LC-MS/MS, the degradation products were identified and possible degradation pathways were proposed. Finally, potential toxicity for PBBPA and generated intermediates were evaluated using luminescent bacteria, which revealed the toxicity of PBBPA was reduced effectively during the photocatalytic degradation process. Overall, the Z-scheme WO3/ZnIn2S4 photocatalyst provides a promising way for the application of photocatalytic technology in actual wastewater treatment.