Ferrous oxalate covered ZVI through ball-milling for enhanced catalytic oxidation of organic contaminants with persulfate

Zero-valent iron (ZVI), with high reduction capacity and cost effectiveness, has been widely used as an activator for persulfate in remediation of organic pollutants. However, the existence of inherent iron oxide shell blocked the transfer of proton and further reduced its reactivity. In present study, a novel persulfate (PS) activator BZVI@OA was synthesized via ball milling ZVI with oxalic acid dihydrate. Scanning electron microscope, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectrometry and Time-of-flight secondary ion mass spectroscopy confirmed the original low proton conductive oxidation shell was replaced by a high proton conductive FeC2O4 shell. The generated shell significantly improved persulfate activated capacity, through which degradation rates of various contaminants were enhanced for 1.64 to 2.33 times. Dissolved oxalate was proved to form complexes with iron ions, dramatically reduced the potential difference and relieved the blocked cyclic conversion. Electron paramagnetic resonance and quenching experiments confirmed an inner sphere adsorption of PS on FeC2O4·2H2O shell which facilitated the peroxide bonds cleavage, leading high efficiency of ROS generation. The accelerated proton transition was confirmed with AC impedance method, resulting in fast and elevated surface bound Fe2+ for persulfate decomposition into active species. Furthermore, BZVI@OA/PS system demonstrated high tolerance over wide initial pH range and promising reusability within 6 cycles. This work clarifies an effective strategy for developing efficient modified ZVI as a PS activator for organic pollutant degradation in water.