Influence of the TiO2 crystalline phase on the performance of UVA/brookite/persulfate and UVA/anatase/persulfate systems for the degradation of isothiazolinones in aqueous matrices

Abstract

The activation of persulfate (PS) under UVA irradiation by two TiO2 polymorphs (brookite and anatase) and titanate photocatalysts was evaluated for the simultaneous removal of the biocides methylisothiazolinone (MIT) and chloromethylisothiazolinone (CMIT), in ultrapure water and real sewage treatment plant water (SW). Titania and titanate samples were synthesized by a hydrothermal method and characterized by XRD, SEM, N2 adsorption-desorption isotherms and UV-Vis DR. The reactions were performed in individual (brookite, anatase, titanate and PS) and hybrid (titania/PS and titanate/PS) systems and compared to those with TiO2-P25 as reference. In ultrapure water, the combined brookite/PS system showed a higher performance for MIT and CMIT abatement and a stronger synergistic effect between titania and PS than found in anatase/PS and titanate/PS systems, indicating the higher effectiveness of the brookite phase for PS activation under UVA. The use of SW water revealed the strong inhibitory effect of matrix constituents in the individual brookite, anatase and PS systems, which exhibited a low performance. However, the kinetics of MIT/CMIT in SW were greatly enhanced in the hybrid TiO2/PS systems, especially with brookite, leading to an efficient degradation of both pollutants and the decrease of total organic carbon (TOC). The addition of chemical scavengers showed a similar reactivity of HO• towards both isothiazolinones whereas a preferential attack of to MIT was observed, demonstrating the selective nature of .