Mechanism of directed activation of peroxymonosulfate by Fe-N/O unsymmetrical coordination-modulated polarized...

Iron-nitrogen co-doped carbon materials as heterogeneous catalysts have attracted much attention in advanced oxidation processes involving peroxymonosulfate (PMS) due to their unique structure and enormous catalytic potential. However, there is limited research on the influence of different coordination structures on the central iron atoms. Through simple pyrolysis, we introduced oxygen atoms into the Fe-N coordination structure, constructing Fe-N/O@C catalysts with Fe-N₂O₂ coordination structure, and achieved efficient degradation of bisphenol A (BPA). Quenching experiments, electron paramagnetic resonance, and electrochemical analysis indicate that compared to the free radical activation pathway of Fe-N@C, high-valent iron-oxo species (≡Fe(Ⅳ) = O) are the main reactive oxygen species (ROS) in the Fe-N/O@C/PMS system. Meanwhile, we compared the differences in the oxidation states of Fe atoms and electron density in different coordination structures, revealing the formation of high-valent iron-oxo species and the mechanism of interfacial electron transfer. Therefore, this study provides new insights into the design and development of Fe-N co-doped catalysts for resource-efficient and environmentally friendly catalytic oxidation systems.