Co-doped Fe3O4/α-FeOOH for highly efficient peroxymonosulfate activation to degrade trimethoprim: Occurrence of hybrid non-radical and radical pathways

Trimethoprim (TMP), as a widely used chemotherapeutic antibiotic agent, has caused potential risks to the aquatic environment. In this study, magnetic Co-doped Fe3O4/alpha-FeOOH was fabricated by a facile one-step ageing method and used for activation of peroxymonosulfate (PMS) in TMP degradation. It was found that low catalyst (0.5 g/L) and PMS addition (0.2 mM) led to the high degradation efficiency of TMP (97.2%, k(obs) = 0.11211 min(-1)) over a wide range of pH. The oxidation of active radical (SO4 center dot(-)) and non-radical singlet oxygen (O-1(2)) co-acted on TMP degradation. Besides, PMS was activated through the cycles between Co(II)/Co(III) and Fe (II)/Fe(III). Fifteen degradation intermediates of TMP were identified by LC-MS, and three possible degradation pathways including hydroxylation, demethylation, and cleavage were proposed. The recovered catalysts exhibited high stability and reusability, maintaining 80% TMP removal efficiency with inappreciable metal leaching (0.012 mg/L of Co, 0.113 mg/L of Fe) after six cycles. Besides, the Co-Fe3O4/alpha-FeOOH/PMS system was highly tolerant to inorganic anions and actual water bodies (river water, lake water, tap water, and sewage plant effluent). Overall, this work provided a promising way to the potential application of Fe-based binary metal oxide for PMS activation.