| Citation: |
FU Xiangyu, LI Yafeng, CUI Keqing, et al. Manganese and phosphorus co-doped corn stover biochar to activate peroxymonosulfate for degradation of norfloxacin[J]. Acta Materiae Compositae Sinica, 2025, 42(4): 2201-2212. DOI: 10.13801/j.cnki.fhclxb.20240702.003
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The large-scale use of antibiotics poses a significant threat to the natural environment and human health, so there is an urgent need to explore an efficient and green degradation method. In this study, Mn/P-doped corn stover biochar (Mn/P-C) was prepared for the degradation of norfloxacin (NOR) by activated permonosulfate (PMS). Compared with pure biochar (BC), P-doped biochar (P-C), Mn/P-C has a larger defect structure and abundant surface oxygen-containing functional groups. Under the conditions of pH=2.84, PMS=3 mmol/L, and catalyst dosing 1 g/L, the NOR removal reached 94% within 80 min reaction time, and the degradation reaction rate of the system was 0.034 min−1. The catalyst characterization, quenching experiments, and electron paramagnetic resonance (EPR) experiments demonstrated that, in the Mn/P-C-activated PMS system, the NOR was mainly removed via SO4•− and O2•− radicals as well as the 1O2 non-radical pathway generated on the catalyst surface were degraded. In addition, Mn/P-C is effective in a wide pH range, has high reusability and stability, and does not cause secondary pollution to the environment due to its good magnetic properties. This study confirms that doping Mn and P can effectively improve the efficacy of biochar-activated PMS for NOR degradation, which provides a new idea for the optimization of carbon-based materials as well as their application in persulfate activation.
With the rapid development of industry and cities in recent years, antibiotic drugs are widely used at home and abroad for the natural environment and human health; overuse will bring about genetic resistance, and antibiotics after discharge will continue to accumulate with the biological chain, which is harmful to the ecological environment. Therefore, strengthening the research on the ecological and environmental harm mechanism of antibiotics, deepening the end-to-end treatment, and reducing the environmental risk of new pollutants such as antibiotics have become the hotspots of wastewater treatment research at home and abroad. In this study, Mn- and P-doped corn stover biochar (Mn/P-C) was prepared for the degradation of norfloxacin (NOR) by activated peroxynitrite (PMS), to optimize the application of biochar catalysts in activated peroxynitrite and to provide a feasible strategy for the degradation of antibiotic organic pollutants in water.
With NOR as the target pollutant, Mn/P-C was prepared by pyrolysis using corn stover, tributyl phosphate (CH)PO, and manganese chloride tetrahydrate MnCl-4HO as raw materials. The structural features of the modified biochar catalyst were analyzed using SEM, XRD, FTIR, and other characterization methods. The structural characteristics of the modified biochar catalyst were combined with the changes of chemical elements in XPS before and after the reaction, the quenching experiments, and electron paramagnetic magnetic resonance (EPR) detection, the potential mechanism of NOR degradation by Mn/P-C activated PMS system was explored. In addition, the effects of different PMS concentrations, catalyst dosages, initial pH values, and common inorganic anions and humic acids in actual water on the degradation efficiency were also investigated.
In this study, Mn and P co-doped biochar (Mn/P-C) was successfully prepared and used as a catalyst to activate PMS to degrade norfloxacin (NOR). It is summarized as follows: (1) Mn/P-C has better adsorption and degradation properties compared with pristine biochar (BC) and P-doped biochar (P-C). (2) From the characterization results of Mn/P-C, it can be seen that the morphology of the catalyst changed dramatically after the successful doping of Mn and P. Stacked and complex folded flakes can be observed, which makes the catalyst have a larger defective structure and abundant surface oxygen-containing functional groups, and provides more activation sites for the degradation of NOR. (3) During the catalytic degradation process, there existed the conversion of Mn(II) to Mn(III) as well as the conversion of Mn(IV) to Mn(III), and the doping of the metal element Mn changed the crystalline composition and elemental distribution of the biochar catalysts, which led to an increase in the active sites of the catalysts, an increase in the electron conduction capacity, and an improvement in the degradation performance. (4) Combining the EPR assay and the quenching reaction, there were both free radicals and non-free radicals in the degradation of NOR by Mn/P-C activated PMS, and the active oxidizing substances that played the leading roles were SO, O, and O. (5) the Mn/P-C catalysts were also effective in a wide range of pH. It is effective in a wide pH range and has high reusability and stability. CO, Cl, and humic acid HA, which are commonly found in water bodies, inhibited the catalytic performance of Mn/P-C.Conclusions: According to "Treating Waste with Waste" , biochar catalysts prepared from natural waste have attracted more research on activated PMS degradation of antibiotic wastewater. In this paper, the successfully prepared Mn/P-C has the characteristics of high catalytic performance, long-lasting free radical generation, and strong catalyst recovery, which can effectively optimize the application of biochar catalyst in activated persulfate and provide a feasible strategy for the degradation of antibiotic organic pollutants in the water body. Maximize the application of biochar catalysts in activating PMS and offer a viable strategy for the degradation of antibiotic organic contaminants in water bodies. The present study provides a systematic and comprehensive analysis to prepare more efficient and cleaner catalysts for activating PMS for NOR degradation, explores the degradation mechanism in the Mn/P-C activated PMS system and proposes a new electron transfer pathway.
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