Targeted degradation of aromatic pollutants in complex matrices via selective electrocatalytic O₂ activation to ¹O₂...

The interference from complex matrices in realistic water environments significantly inhibits the degradation kinetics of target pollutants. Herein, we propose an electronic reconfiguration strategy by introducing O into the coordination sphere of Fe-N₄-C sites (Fe-NC(O)) to achieve selective electrocatalytic O₂ activation to singlet oxygen (¹O₂). The electrophilic ¹O₂ can selectively degrade of electron-rich compounds. Mechanistic studies reveal that the electron-withdrawing O depletes the valence electron density in the d-orbitals of Fe, thereby weakening *OOH adsorption to inhibit O-O bond scission. Consequently, Fe-NC(O) achieves a 22.45-fold enhancement in ¹O₂ yield compared to the Fe single atom catalyst without O doping. Notably, ¹O₂ accounts for 93 % of the total reactive oxygen species in the Fe-NC(O) system. The Fe-NC(O) achieves rapid degradation of aromatic pollutants (phenol, bisphenol A, p-chlorophenol, and sulfamethoxazole) with high mineralization efficiency (>80 %) in wastewater containing coexisting natural organic matter and inorganic ions. Furthermore, it realizes the energy-efficient decontamination of real medical wastewater with a specific energy consumption of only 6.85 kWh kg_(COD)^-1. This work demonstrates a feasible strategy for efficient ¹O₂ production, advancing electrochemical advanced oxidation processes for water decontamination.