Photocatalytic degradation of alkyl imidazole ionic liquids by TiO2 nanospheres under simulated solar irradiation: Transformation behavior, DFT calculations and promoting effects of alkali and alkaline earth metal ions

In this study, TiO2 nanospheres prepared by the sol-gel method were found to efficiently catalyze the photodegradation of 1-butyl-2,3-dimethylimidazolium bromide salt ([BMMIm]Br) under simulated solar irradiation through the main attack of hydroxyl radicals (•OH). The promoting effect of alkali metal (Li+→Cs+) and alkaline earth metal ions (Mg2+→Ba2+) was particularly emphasized. In-situ EPR tests showed that the introduction of alkali and alkaline earth metal ions could enhance the formation of •OH thus leading to a 7%-30.3% increase in the degradation efficiency of. [BMMIm]+. Moreover, the removal efficiency of [BMMIm]+ still reached > 96.19% in four real waters. A total of 23 products of [BMMIm]Br were detected, and hydroxyl substitution, bond breaking, direct oxidation and ring opening were considered as the main reactions during the photocatalytic degradation process. The results of toxicity evaluation showed that hydroxylation was a reaction process of increasing toxicity, while the bond breaking reaction had great detoxification capacity for [BMMIm]+. These findings may enhance our understanding on the effects of alkali or alkaline earth metal ions on the photocatalytic activity of TiO2, which could also provide reference for the efficient and green removal of alkylimidazolium ionic liquids in waters.