Enhanced Photooxidation of Hydroquinone by Acetylacetone, a Novel Photosensitizer and Electron Shuttle

Quinones are important electron shuttles as well as micropollutants in the nature. Acetylacetone (AA) is a newly recognized electron shuttle in aqueous media exposed to UV irradiation. Herein, we studied the interactions between AA and hydroquinone (QH₂) under steady-state and transient photochemical conditions to clarify the possible reactions and consequences if QH₂ and AA coexist in a solution. Steady-state experimental results demonstrate that the interactions between AA and QH₂ were strongly affected by dissolved oxygen. In O₂-rich solutions, the phototransformation of QH₂ was AA-independent. Both QH₂ and AA utilize O₂ as the electron acceptor, but in O₂-insufficient solutions, AA became an important electron acceptor for the oxidation of QH₂. In all cases, the coexistence of AA increased the phototransformation of QH₂, whereas the decomposition of AA in O₂-saturated and oversaturated solutions was inhibited by the presence of QH₂. The underlying mechanisms were investigated by a combination of laser flash photolysis (LFP) and reduction potential analysis. The LFP results show that the excited AA serves as a better electron shuttle than QH₂. As a consequence, AA might regulate the redox cycling of quinones, leading to significant effects on many processes, ranging from photosynthesis and respiration to photodegradation.