Synergistic removal mechanism of tetracycline by ethylenediamine modified magnetic chitosan based Fenton-like catalyst†

Modified magnetic chitosan nanoparticles (EMMCS-G), used as a Fenton-like catalyst, were successfully prepared and modified with glutaraldehyde and ethylenediamine. EMMCS-G has strong magnetization, good reusability, stability, environmental friendliness, and high efficiency. In the Fenton-like system, the synergistic effect of adsorption and advanced oxidation significantly enhances the removal effect of tetracycline (TC). The optimal concentration of persulfate was found to be 20 mmol L⁻¹, and at a pH of 3, the removal efficiency of TC reached 95.6% after 6 hours. The oxidation system demonstrated excellent pH adaptability, achieving a TC removal rate of 94% within 6 hours across a pH range of 3 to 8. Hydroxyl (˙OH) and sulfate (SO₄⁻˙ ) radicals were present in the reaction system, with ˙OH playing an important role in the oxidation process of TC. The attack sites of tetracycline were identified using density functional theory (DFT), and five degradation pathways for TC were proposed based on LS-MS experiments. Finally, quantitative structure–activity relationship (QSAR) analysis was employed to assess the toxicity of the intermediates. Overall, toxicity gradually decreased, indicating that the Fenton reaction system effectively reduced the toxicity and mutagenicity of TC. This study suggests EMMCS-G as a potential catalyst for enhanced Fenton-like degradation with excellent efficiency observed for the degradation of tetracycline for environmental remediation.