Fe-Ce based metal-organic framework as a novel heterogeneous catalyst accelerating redox cycle for efficient degradation of sulfamethoxazole in wide pH ranges

Abstract

The electro-Fenton (EF) technology holds immense potential for wastewater treatment. However, there persist certain factors that affect its degradation efficiency, such as the restricted pH range, production of iron sludge and sluggish conversion rate between Fe2+ and Fe3+. Herein, 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) was introduced as the organic ligand to synthesize a series of efficient iron-based MOF catalysts (FexCe1-HHTP (x = 1, 2, 3, 4)) with different molar ratios for sulfamethoxazole (SMX) degradation in heterogeneous EF system. HHTP with electron-rich functional groups is beneficial to enhance performance of oxygen evolution reaction. Among these catalysts, Fe3Ce1-HHTP catalyst achieved 97.3 % degradation efficiency in 30 min and mineralization rate was 89.7 % at 1 h. The introduction of Ce promoted the transition of Fe3+ and Fe2+ in heterogeneous EF reaction. The synergistic effects between Fe3+/Fe2+ and Ce4+/Ce3+ further catalyzed the generation of hydroxyl radicals and it was proved as the main active species. The heterogeneous catalyst showed good performance in wide pH range, good stability, and high degradation efficiency to other pollutants. Three possible SMX degradation routes are suggested on basis of intermediates detected by mass spectrum analysis and theoretical calculations. The toxicity of these intermediates was assessed using Toxicity Estimation Software Tool (T.E.S.T.). This work provides valuable guidance for the design of highly efficient and stable heterogeneous EF catalyst for antibiotic degradation and expand the application potential in wastewater treatment of organic pollutants.