Iron/nitrogen co-doped biochar derived from salvaged cyanobacterial for efficient peroxymonosulfate activation and ofloxacin degradation: Synergistic effect of Fe/N in non-radical path.

A green, low-cost, high-performance Fe/N co-doped biochar material (Fe-N@C) was synthesized using salvaged cyanobacteria without other extra precursors for peroxymonosulfate (PMS) activation and ofloxacin (OFX) degradation. With the increased pyrolysis temperature, the graphitization degree, the specific surface area and the corresponding groups like OH, COO etc. for Fe-N@C tended to increase, resulting in a greater OFX adsorption. However, the total amount of Fe-N and graphitic nitrogen groups in the Fe-N@C composites was firstly increased and then decreased, which reached the highest at 800 °C (Fe-N@C-800). All these changes of functional species ascribed to the strong interaction between Fe, N and C led to the highest defect degree of Fe-N@C-800, resulting the highest OFX removal efficiency of 95.0 %. OFX removal experiments indicated the adsorption process promoted the total OFX degradation for different functional groups on Fe-N@C composites separately dominated the process of OFX adsorption and PMS catalysis. Radical quenching and electron paramagnetic resonance (EPR) measurements proved free radical and non-free radical pathways participated in Fe-N@C/PMS system. The non-free radicals based on O and high-valent iron-oxo species played a more important role in OFX degradation, leading to the minimal effect of co-existing anions and the high universality for other antibiotic pollutants. Fe-N was utilized as the main catalytic sites and graphitic nitrogen contributed more to the electron transfer for PMS activation, whose synergistic effect efficiently facilitated OFX degradation. Finally, the possible degradation route of OFX in the Fe-N@C-800/PMS system was proposed. All these results will provide the new insights into the intrinsic mechanism of Fe/N species in carbon-based materials for PMS activation.