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-NX 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 1O2 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-NX 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.

Peroxymonosulfate activation by Fe-N-S co-doped tremella-like carbocatalyst for degradation of bisphenol A: Synergistic effect of pyridine N, Fe-Nx, thiophene S.

Bisphenol A (BPA) has received increasing attention due to its long-term industrial application and persistence in environmental pollution. Iron-based carbon catalyst activation of peroxymonosulfate (PMS) shows a good prospect for effective elimination of recalcitrant contaminants in water. Herein, considering the problem about the leaching of iron ions and the optimization of heteroatoms doping, the iron, nitrogen and sulfur co-doped tremella-like carbon catalyst (Fe-NS@C) was rationally designed using very little iron, S-C3N4 and low-cost chitosan (CS) via the impregnation-calcination method. The as-prepared Fe-NS@C exhibited excellent performance for complete removal of BPA (20 mg/L) by activating PMS with the high kinetic constant (1.492 min-1) in 15 min. Besides, the Fe-NS@C/PMS system not only possessed wide pH adaptation and high resistance to environmental interference, but also maintained an excellent degradation efficiency on different pollutants. Impressively, increased S-C3N4 doping amount modulated the contents of different N species in Fe-NS@C, and the catalytic activity of Fe-NS@C-1-x was visibly enhanced with increasing S-C3N4 contents, verifying pyridine N and Fe-Nx as main active sites in the system. Meanwhile, thiophene sulfur (C-S-C) as active sites played an auxiliary role. Furthermore, quenching experiment, EPR analysis and electrochemical test proved that surface-bound radicals (·OH and SO4⋅-) and non-radical pathways worked in the BPA degradation (the former played a dominant role). Finally, possible BPA degradation route were proposed. This work provided a promising way to synthesize the novel Fe, N and S co-doping carbon catalyst for degrading organic pollutants with low metal leaching and high catalytic ability.