Ultra-uniform MIL-88B(Fe)/Fe3S4 hybrids engineered by partial sulfidation to boost catalysis in electro-Fenton treatment of micropollutants: Experimental and mechanistic insights

Abstract

Fe-based metal-organic frameworks are promising catalysts for water treatment, although their viability is hampered by the slow regeneration of active Fe(II) sites. A facile sulfidation strategy is proposed to boost the catalytic activity of MIL-88B(Fe) in heterogeneous electro-Fenton (HEF) treatment of organic micropollutants at mild pH. The synthesized MIL-88B(Fe)/Fe3S4 hybrids possessed numerous and durable unsaturated iron sites, acting the S2- atoms as electron donors that enhanced the Fe(II) recycling. The sulfidated catalyst outperformed the MIL-88B(Fe), as evidenced by the 7-fold faster degradation of antibiotic trimethoprim by HEF and the fast destruction of micropollutants in urban wastewater. The hybrid catalyst was reused, obtaining >90% drug removal after four runs and, additionally, its inherent magnetism facilitated the post-treatment recovery. Electrochemical tests and DFT calculations provided mechanistic insights to explain the enhanced catalysis, suggesting that the accelerated Fe(III)/Fe(II) cycling and the enhanced mass transport and electron transfer accounted for the efficient trimethoprim degradation.