Synergetic Oxidation of the Hydroxyl Radical and Superoxide Anion Lowers the Benzoquinone Intermediate Conversion Barrier and Potentiates Effective Aromatic Pollutant Mineralization

Regulation of the free radical types is crucial but challenging in the ubiquitous heterogeneous catalytic oxidation for chemosynthesis, biotherapy, and environmental remediation. Here, using aromatic pollutant (AP) removal as a prototype, we identify the massive accumulation of the benzoquinone (BQ) intermediate in the hydroxyl radical ( • OH)-mediated AP degradation process. Theoretical prediction and experiments demonstrate that BQ is both a Lewis acid and base because of its unique molecular and electronic structure caused by the existence of symmetrical carbonyl groups; therefore, it is hard to be electrophilically added by oxidizing • OH as a result of the high reaction energy barrier (Δ G = 1.74 eV). Fortunately, the introduction of the superoxide anion ( • O 2 – ) significantly lowers the conversion barrier (Δ G = 0.91 eV) of BQ because • O 2 – can act as the electron donor and acceptor simultaneously, electrophilically and nucleophilically add to BQ synchronously, and break it down. Subsequently, the breakdown products can then be further oxidized by • OH until completely mineralized. Such synergistic oxidation based on • OH and • O 2 – timely eliminates BQ, potentiates AP mineralization, and inhibits electrode fouling caused by high-resistance polymeric BQ; more importantly, it effectively reduces toxicity, saves energy and costs, and decreases the environmental footprint, evidenced by the life cycle assessment.