Ubiquitous oxygen vacancies (Vo) existing in metallic compounds can activate peroxymonosulfate (PMS) for water treatment. However, under environmental conditions, especially oxygenated surroundings, the interactions between Vo and PMS as well as the organics degradation mechanism are still ambiguous. In this study, we provide a novel insight into the PMS activation mechanism over Vo-containing Fe-Co layered double hydroxide (LDH). Experimental results show that Vo/PMS is capable of selective degradation of organics via a single-electron-transfer nonradical pathway. Moreover, O₂ is firstly demonstrated as the most critical trigger in this system. Mechanistic studies reveal that, with abundant electrons confined in the vacant electron orbitals of Vo, O₂ is thermodynamically enabled to capture electrons from Vo to form O₂^•- under the imprinting effect and start the activation process. Simultaneously, Vo becomes electron-deficient and withdraws the electrons from organics to sustain the electrostatic balance and achieve organics degradation (32% for Bisphenol A without PMS). Different from conventional PMS activation, under the collaboration of kinetics and thermodynamics, PMS is endowed with the ability to donate electrons to Vo as a reductant other than an oxidant to form ¹O₂. In this case, ¹O₂ and O₂^•- act as the indispensable intermediate species to accelerate the circulation of O₂ (as high as 14.3 mg/L) in the micro area around Vo, and promote this nano-confinement electron-recycling process with 67% improvement of Bisphenol A degradation. This study provides a brand-new perspective for the nonradical mechanism of PMS activation over Vo-containing metallic compounds in natural environments.

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