Mn-NSC co-doped modified biochar/permonosulfate system for degradation of ciprofloxacin in wastewater

Abstract

Mn-Nitrogen-sulfur co-doped modified biochar (Mn-NSCX) is prepared by high-temperature pyrolysis and hydrothermal method, and its properties are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). A metal-non-technical co-doping system was constructed and first used for PMS activation towards ciprofloxacin degradation. The results show that doping of Mn, N and S significantly improve the catalytic performance of activated PMS to degrade CIP, among which Mn-NSC2 exhibit the best catalytic performance, when the dosage of MN-NSC2 is 0.4 g·L−1, the concentration of PMS is 0.4 mmol·L−1, and the concentration of CIP is 20 mg·L−1. After 60 min, more than 99% of CIP can be removed, among which the CIP removal rate of BC/PMS is 43.6%, and the CIP removal rate of NSC5/PMS is 50.3%. The removal effect of CIP is greatly improved after the incorporation of manganese, attributing to the oxidation reaction between the PMS and manganese dioxide. The results of electron paramagnetic resonance (EPR) indicate that both free radicals (·SO4-,·OH) and non-free radicals (1O2) play important roles in the degradation of CIP, and 1O2 plays a foremost role in the degradation of CIP. Doping of Mn, N and S accelerate the electron transfer rate and improve the catalytic activity of the material. In this paper, the loading of metal oxides can increase the corresponding catalytic sites and promote electron transfer, thus promoting the ability of activated PMS to degrade organic pollutants. The metal modification not only improves the oxygen-containing groups of the material, but also promotes the activation of persulfate by metal oxidation on the surface of the material. A novel design and preparation strategy for catalyst is proposed to simultaneously achieve stable Mn-Nitrogen-sulfur co-doped modified biochar and improve the catalytic performance of biochar by adding Mn, S, and N.