Insight into iron oxychloride composite bone char for peroxymonosulfate activation: Mechanism of singlet oxygen evolution for selective degradation of organic pollutants

Abstract

The activity of iron-based catalysts in advanced oxidation processes (AOPs) is limited by the redox cycle of Fe(III) and Fe(II). In this work, iron oxychloride (FeOCl) with a unique layered structure was loaded on the bone char (BC) to enhance the activation of peroxymonosulfate (PMS). Characterization of the FeOCl-BC catalyst reveals that the loading of FeOCl changed the composition and structure of BC and BC reduced the bond gap of FeOCl. Acetaminophen (APAP) as a target pollutant could be almost completely degraded at neutral pH, and the removal rate reached 0.6597 min−1. APAP could also be selectively oxidized by FeOCl-BC/PMS system in the presence of some inorganic anions (SO42−, NO3−, and Cl−) and humic acid. Quenching experiments, electron paramagnetic resonance (EPR), chemical probes, and linear sweep voltammetry (LSV) confirm that the primary oxidation mechanism of the FeOCl-BC/PMS system was dominated by 1O2. The 1O2 was generated from the conversion of O2•− and the self-dissociation of PMS, involving the formation of metastable iron intermediates and the redox cycle of Fe(III) and Fe(II). The unique structure of FeOCl, the transport of lattice oxygen and the enrichment of electrons by carbon defects play an essential role in generating reactive species. In this work, the limitation of the redox cycle of Fe(III) and Fe(II) was broken by loading FeOCl on the surface of BC, and a new catalytic mechanism was proposed. This work provides a new perspective for the construction of efficient iron-based catalysts and the practical application of PMS-based AOPs.