Low-coordinated Co-N3 sites induce peroxymonosulfate activation for norfloxacin degradation via high-valent cobalt-oxo species and electron transfer

Abstract

The identification of reactive species in peroxymonosulfate (PMS) activation triggered by carbon-based single atom catalysts is the key to reveal the pollutant degradation mechanism. Herein, carbon-based single atom catalyst with low-coordinated Co-N₃ sites (Co_SA-N₃-C) was synthesized to active PMS for norfloxacin (NOR) degradation. The Co_SA-N₃-C/PMS system exhibited consistent high performance for oxidizing NOR over a wide pH range (3.0-11.0). The system also achieved complete NOR degradation in different water matrixes, high cycle stability and excellent degradation performance for other pollutants. Theoretical calculations confirmed that the catalytic activity was derived from the favorable electron density of low-coordinated Co-N₃ configuration, which was more conductive to PMS activation than other configurations. Electron paramagnetic resonance spectra, in-situ Raman analysis, solvent exchange (H₂O to D₂O), salt bridge and quenching experiments concluded that high-valent cobalt(IV)-oxo species (56.75%) and electron transfer (41.22%) contributed dominantly to NOR degradation. Moreover, ¹O₂ was generated in the activation process while not involved in pollutant degradation. This research demonstrates the specific contributions of nonradicals in PMS activation over Co-N₃ sites for pollutant degradation. It also offers updated perceptions for rational design of carbon-based single atom catalysts with appropriate coordination structure.

Keywords: Coordination configuration; Nonradical pathway; Norfloxacin degradation; Peroxymonosulfate activation; Single atom catalyst.