Accelerating Fe(III)/Fe(II) redox cycling in heterogeneous electro-Fenton process via S/Cu-mediated electron donor-shuttle regime

In this study, we developed a Cu0.5Fe2.5S4 nanocatalyst through facile sulfidation of the Cu-MIL-88B(Fe) precursor to expedite surface Fe(III) reduction and enhance H2O2 activation in the heterogeneous electro-Fenton (HEF). The as-prepared catalyst possesses relatively large specific surface area and uniformly dispersed metal active sites. The Cu0.5Fe2.5S4 catalyzed HEF system allowed compete removal of naproxen with minimal metal leaching, surpassing that of Cu-MIL-88B(Fe) or Fe3S4. Quantitative XPS analysis, electrochemical characterization and density functional theory calculations elucidate an electron donor-shuttle regime that S2- and Cu species serve as the electron donor and shuttle, respectively. The Cu species significantly accelerate the internal electron transfer between S and Fe and mitigate the dissolution of the adjacent iron sites, securing the sustainable reducing capacity. Moreover, Cu0.5Fe2.5S4-based HEF exhibits great practicability for treatment of various organics in urban wastewater. This study opens new avenue for addressing the challenge of sluggish Fe(III)/Fe(II) cycling in HEF.