Amino polycarboxylic acid complex agent modified Fe0 enhanced activation of H2O2 double decomposition pathways for tetracycline removal under neutral condition

Abstract

The summary of this study explores the modification of Fe0 with amino polycarboxylic acid complex agents (APCAs) to enhance H2O2 catalysis for tetracycline (TC) removal under neutral conditions. The ethylenediaminetetraacetic acid-modified Fe0/H2O2 system (EDTA-Fe0/H2O2) achieved a removal efficiency of 90.2 % for 50 mg/L TC, significantly higher than the 23.9 % efficiency of the traditional Fe0/H2O2 system. The removal rate of various pollutants by the EDTA- Fe0/H2O2 process is 2.9 to 8.4 times higher than that of the Fe0/H2O2 process. After four cycles of use, the removal rate of TC by the EDTA-Fe0/H2O2 system can still reach 76.3 %. Additionally, the effect of treating TC in natural freshwater can also achieve 80.1 %. Characterization revealed that EDTA-Fe0 had a larger Fe(II) proportion, better hydrophobicity, and lower corrosion potential than Fe0, indicating higher activity. Quenching experiments and electron paramagnetic resonance tests confirmed that •OH was the major reactive species. Shell-isolated nanoparticle-enhanced Raman spectroscopy indicated the presence of *OOH species, suggesting the involvement of a dioxygen coordination reaction. Density functional theory calculations showed that both dioxygen and single oxygen coordination H2O2 decomposition pathways played significant roles, and EDTA-Fe0 exhibited high catalysis ability for H2O2 in both pathways. Analysis of the relationship between APCAs’ group structure and APCAs-Fe0 properties indicated that the number of carboxyl groups was crucial for enhancing catalytic activity, while the number of amino groups also impacted antibiotic removal efficiency. Overall, this study provides a solid theoretical foundation for further Fe0 applications and suggests a new method to improve TC removal.