Copper substituted zinc ferrite with abundant oxygen vacancies for enhanced ciprofloxacin degradation via peroxymonosulfate activation

In this paper, copper substituted zinc ferrite (ZCFO) catalyst with rich oxygen vacancies (OVs) was synthesized via a simple one pot sol-gel combustion method, and firstly used for peroxymonosulfate (PMS) activation to degrade a typical antibiotic ciprofloxacin (CIP). Only ∼15 min was required to achieve 96.6% of CIP degradation using ZCFO as the catalyst, and the pseudo-first-order reaction constant was about 95 times higher than that of conventional zinc ferrite (1.90 min−1 vs 0.02 min−1). ZCFO catalyst showed great stability and reusability based on the successive degradation cycles and could be easily recovered through magnetic separation. Besides, the effects of catalyst loading, PMS concentration, reaction temperature, initial solution pH, coexisting anions and humic acid (HA) on CIP degradation were systematically investigated. Radical quenching tests and electron paramagnetic resonance (EPR) revealed that sulfate radical (SO4-.), hydroxyl radical (OH∙), superoxide radical (O2∙-) and singlet oxygen (1O2) were involved in the ZCFO/PMS system, among which O2∙- and 1O2 were the dominant reactive oxygen species (ROS). The excellent catalytic activity of ZCFO was ascribed to the dual active sites of Fe and Cu and large amount of OVs after Cu substitution, which was beneficial to generate ROS for CIP removal.