Heterogeneous Fenton-like removal of tri(2-chloroisopropyl) phosphate by ilmenite (FeTiO3): Kinetic, degradation mechanism and toxic assessment

Abstract

Tri(2-chloroisopropyl) phosphate (TCPP), a common organophosphate flame retardant, was frequently detected in the environment and posed threats to human health. In this work, the main component of ilmenite FeTiO₃ was synthesized by the sol-gel method and employed as the catalyst for the degradation of TCPP by activating persulfate (PS) under UV irradiation. The degradation processes were fitted by the pseudo-first-order kinetic. The k_obs value in UV/FeTiO₃/PS system was up to 0.0056 min^-1 and much higher than that in UV/PS (0.0014 min^-1), UV/FeTiO₃ (0.0012 min^-1) and FeTiO₃/PS (0.0016 min^-1) systems, demonstrating a distinct synergistic effect in TCPP removal. The degradation efficiency of TCPP increased with the increase of UV intensity, PS concentration and catalyst dosage, and with the decrease of pH. By quenching experiment and EPR analysis, ·OH was confirmed to be the dominant radical in the reaction of the UV/FeTiO₃/PS system. The possible degradation pathways of TCPP were dechlorination, dealkylation, and further oxidation of alkyl groups based on the theoretical calculation of frontier molecular orbits. The toxicity of degradation intermediates evaluated by luminescence inhibition rate of photoluminescence was higher than TCPP. Thus, TCPP can be degraded in the UV/FeTiO₃/PS system effectively at the premise of introducing controlling measures to reduce the toxicity of degradation intermediates.

Keywords: Catalytic degradation; FeTiO(3); Mechanisms; Persulfate; Tri(2-chloroisopropyl) phosphate.