Surface reconstructed Fe@C for enhanced Fenton-like catalysis: Sustainable ciprofloxacin degradation and toxicity reduction.

The Fe-based catalysts typically undergo severe problems such as deactivation and Fe sludge emission during the peroxymonosulfate (PMS) activation, which commonly leads to poor operation and secondary pollution. Herein, an S-doped Fe-based catalyst with a core-shell structure (Fe@C, T = 1000°C) was synthesized, which can solve the above issues via the dynamic surface evolution during the reaction process. Specifically, the Fe on the surface of Fe@C could be consumed rapidly, leaving numerous pores; the FeC from the core would subsequently migrate to the surface of Fe@C, replenishing the consumed active Fe species. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses demonstrated that the reaction surface reconstructed during the PMS activation, which involved the Fe in-situ reduction by S species as well as the depletion/replenishment of effective Fe species. The reconstructed Fe@C achieved near-zero Fe sludge emission (from 0.59 to 0.08-0.23 mg L) during 5 cycles and enabled the dynamic evolution of dominant reactive oxygen species (ROS) from SO to FeO, sustainably improving the oxidation capacity (80.0-92.5% in following four cycles) to ciprofloxacin (CIP) and reducing the toxicity of its intermediates. Additionally, the reconstructed Fe@C/PMS system exhibited robust resistance to complex water matrix. This study provides a theoretical guideline for exploring surface reconstruction on catalytic activity and broadens the application of Fe-based catalysts in the contaminants elimination.