Fe-N-C catalyst with Fe-NX sites anchored nano carboncubes derived from Fe-Zn-MOFs activate peroxymonosulfate for high-effective degradation of ciprofloxacin: Thermal activation and catalytic mechanism

Abstract

Developing high-efficient catalysts is crucial for activating peroxymonosulfate (PMS). Fe-N-C catalysts exhibit excellent performance for PMS activation because of the contribution of doped N, Fe-Nx and Fe₃C sites. In our work, a series of Fe-N-C catalysts with high-performance was obtained by pyrolyzing Fe-Zn-MOFs precursors. During pyrolysis process, the change of chemical bonds and formation of active sites in the precursor were elucidated by characterization analysis and related catalytic experiments. Graphitic N, Fe-Nx and Fe₃C were confirmed to activate PMS synergistically for ciprofloxacin (CIP) degradation. Besides, the catalytic performance was proportional to the amount of doped iron and calcination temperature. Moreover, the Fe-N-C-3-800/PMS system not only displayed good recycling performance, but also had high anti-interference ability. Integrated with quenching and electron paramagnetic resonance (EPR) experiments, a non-radical pathway dominated by ¹O₂ was proposed. Furthermore, PMS could bond to Fe-N-C-3-800 to form intermediate for charge transfer, thus accelerate electron transfer between CIP and PMS to realize degradation of CIP. Six main pathways of CIP degradation were proposed, which include bond fission of N-C on piperazine ring and direct oxidation of CIP. This study provided a new idea for the design of heterogeneous carbon catalysts in advanced oxidation field.

Keywords: CIP degradation; Electron transfer mechanism; Fe-N-C catalyst; Peroxymonosulfate; Pyrolysis.