The Surface Confinement of FeO Assists in the Generation of Singlet Oxygen and High‐Valent Metal‐Oxo Species for Enhanced Fenton‐Like Catalysis

Abstract Transition metal compounds (TMCs) have long been potential candidate catalysts in persulfate‐based advanced oxidation process (PS‐AOPs) due to their Fenton‐like catalyze ability for radical generation. However, the mechanism involved in TMCs‐catalyzed nonradical PS‐AOPs remains obscure. Herein, the growth of FeO on the Fe 3 O 4 /carbon precursor is regulated by restricted pyrolysis of MIL‐88A template to activate peroxymonosulfate (PMS) for tetracycline (TC) removal. The higher FeO incorporation conferred a 2.6 times higher degradation performance than that catalyzed by Fe 3 O 4 and also a higher interference resistance to anions or natural organic matter. Unexpectedly, the quenching experiment, probe method, and electron paramagnetic resonance quantitatively revealed that the FeO reassigned high nonradical species ( 1 O 2 and Fe IV═O ) generation to replace original radical system created by Fe 3 O 4 . Density functional theory calculation interpreted that PMS molecular on strongly‐adsorbed (200) and (220) facets of FeO enjoyed unique polarized electronic reception for surface confinement effect, thus the retained peroxide bond energetically supported the production of 1 O 2 and Fe IV═O . This work promotes the mechanism understanding of TMCs‐induced surface‐catalyzed persulfate activation and enables them better perform catalytic properties in wastewater treatment.