Photoelectrocatalytic Degradation of Tetracycline Using Covalent Organic Frameworks Under Neutral Conditions

The elimination of antibiotics such as tetracycline from wastewater under neutral conditions is of great significance, yet it remains a challenge. Here, a methoxy‐functionalized pyrene‐based covalent organic framework (Py‐OCH 3 ‐COF) was synthesized and employed to construct a photoelectrocatalytic (PEC) system for the tetracycline (TC) degradation. The TC degradation performance was systematically evaluated under three different conditions, namely electrocatalysis (EC), photocatalysis (PC), and PEC under visible light irradiation, respectively. Among them, under the PEC condition, the Py‐OCH 3 ‐COF exhibited the highest performance, achieving a TC degradation efficiency of 89.39% within 60 min. The corresponding reaction rate constant in the PEC process reaches 0.039 min −1 , almost 1.86 and 13 times higher than those in the EC and PC processes, respectively, indicating a significant PEC synergistic effect. Radical trapping experiments and electron paramagnetic resonance analysis revealed that the enhanced PEC performance originates from a pronounced PEC synergy that promotes charge separation and modulates the reactive oxygen species distribution, rendering singlet oxygen ( 1 O 2 ) the dominant reactive species. The corresponding intermediates generated during TC degradation, identified using liquid chromatography‐mass spectrometry, further enable the proposal of plausible degradation pathways. This study provides a feasible and green strategy for the efficient treatment of organic wastewater under neutral conditions.