Effect of pyrolysis temperature on the activated permonosulfate degradation of antibiotics in nitrogen and sulfur-doping biochar: Key role of environmentally persistent free radicals

Because of the increasingly widespread contamination of antibiotics, the preparation of biochar by heteroatom doping to further improve the catalytic degradation efficiency of antibiotics has become a major focus of research. In this study, N-doped (NBC), S-doped (SBC), and NS-doped (NSBC) moso bamboo biochar were obtained at preparation temperatures of 300–700 °C. The concentration of environmentally persistent free radicals (EPFRs) in all biochars peaked when the preparation temperature was 500 °C: 2.45 × 10¹⁹ spins·g⁻¹ (BC), 9.23 × 10¹⁹ spins·g⁻¹ (NBC), 6.10 × 10¹⁹ spins·g⁻¹ (SBC), and 4.36 × 10¹⁹ spins·g⁻¹ (NSBC). After heteroatom doping, EPFR species were more abundant, and the distribution of three types of EPFRs (oxygen-centered (g > 2.0040), carbon-centered (g < 2.0030), and carbon-centered radicals with oxygen atom free radicals (2.0030 < g < 2.0040) varied with the preparation temperature. In the process of antibiotic degradation, both NBC and SBC increased the degradation rate of antibiotics, whereas NSBC reduced the degradation rate. Compared with the degradation rate of antibiotics of biochar (79.86%), the degradation rate of antibiotics by NBC, SBC, and NSBC via PMS activation was 92.23%, 88.86%, and 70.97% on average in 30 min, respectively. The greatest contributors to the catalytic degradation were SO₄•⁻, followed by ¹O₂, •OH, and O₂•⁻. EPFRs and ¹O₂ might be the main contributors to the free radical and non-free radical pathways. The enhancement of EPFRs following the N doping or S doping of biochar is the key factor underlying PMS activation. Therefore, changes in the structure of biochar can better activate PMS to produce reactive oxygen species-degrading antibiotics. The mineralization rate of antibiotics by BC, NBC, SBC, and NSBC was 42.12%, 47.06%, 44.99%, and 39.01%, respectively. This means that a small portion of the antibiotics was completely decomposed into CO₂, H₂O, and inorganic substances after degradation. Cyclic experiments showed that heteroatom-doped biochar had higher reusability, and the degradation rate decreased less than 15%.