Manganese and phosphorusco-doped corn stover biochar to activate peroxymonosulfate for degradation of norfloxacin
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摘要: 抗生素的大规模使用对自然环境及人类健康造成极大威胁，因此急需探寻一种高效、绿色的降解方法。本研究制备了Mn、P掺杂玉米秸秆生物炭(Mn/P-C)用于活化过一硫酸盐(PMS)降解诺氟沙星(NOR)。对比纯生物炭(BC)、P掺杂生物炭(P-C)，Mn/P-C具有更大的缺陷结构及丰富的表面含氧官能团。在pH为2.84、PMS为3 mmol/L、催化剂投加量为1 g/L的条件下，80 min反应时间内，NOR去除率达到94%，体系降解反应速率为0.034 min−1。催化剂表征、淬灭实验和电子顺磁共振(EPR)实验表明，在Mn/P-C活化PMS体系中，NOR主要通过SO4•−、O2•−自由基以及催化剂表面产生的1O2非自由基途径得到降解。此外，Mn/P-C在较宽的pH范围内均有效，并且具有较高的可重复利用性和稳定性，由于其良好的磁性，不会对环境造成二次污染。本研究证实了掺杂Mn、P可以有效提高生物炭活化PMS降解NOR的效能，为碳基材料的优化以及其在过硫酸盐活化中的应用提供了新的思路。Abstract: 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.
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Key words:
- manganese/phosphorus doping /
- biochar /
- advanced oxidation /
- persulfate activation /
- norfloxacin
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图 1 生物炭(BC)(a)、P掺杂生物炭(P-C)(b)、Mn、P掺杂玉米秸秆生物炭(Mn/P-C)(c)的SEM 图像
Figure 1. SEM images of biochar (BC) (a), P-doped biochar (P-C) (b), Mn, P-doped corn stover biochar (Mn/P-C) (c)
图 2 (a)BC, P-C和 Mn/P-C的XRD谱图、(b)FTIR图谱、(c)XPS全谱图、(d)拉曼光谱
Figure 2. (a)XRD spectra, (b)FTIR spectra, (c) XPS spectra ,(d) Raman spectra of BC, P-C and Mn/P-C
图 3 BC, P-C和 Mn/P-C对NOR的吸附去除率(a)、对应的吸附反应速率常数(b)。反应条件：PMS = 1.5 mmol/L, BC、P-C、Mn/P-C = 1 g/L,NOR = 10 mg/L, pH=6
Figure 3. (a) XRD spectra, (b) FTIR spectra of BC, P-C and Mn/P-C.Reaction conditions:PMS = 1.5 mmol/L, BC、P-C、Mn/P-C = 1 g/L,NOR = 10 mg/L, pH=6
图 4 (a) BC, P-C和 Mn/P-C对NOR的降解去除率、(b)相应的降解反应速率常数。反应条件：PMS = 1.5 mmol/L, BC、P-C、Mn/P-C = 0.5 g/L,NOR = 10 mg/L, pH=6
Figure 4. (a) The degradation removal rate of NOR caused by BC, P-C and Mn / P-C, (b) The corresponding degradation reaction rate constants. Reaction conditions: PMS = 1.5 mmol/L, BC、P-C、Mn/P-C = 0.5 g/L, NOR = 10 mg/L, pH=6
图 5 (a) Mn/P-C 投加量对NOR降解的影响，反应条件：PMS = 1.5 mmol/L、pH=6、NOR = 10 mg/L；(b) PMS浓度对NOR降解的影响，反应条件：Mn/P-C = 0.5 g/L、pH=6、NOR = 10 mg/L
Figure 5. (a) Effect of Mn/P-C dosage for NOR degradation, Reaction conditions: PMS = 1.5 mmol/L、pH=6、NOR = 10 mg/L; (b) PMS concentrations for NOR degradation, Reaction conditions: Mn/P-C = 0.5 g/L、pH=6、NOR = 10 mg/L
图 6 (a) pH值对NOR降解的影响，反应条件：Mn/P-C =1 g/L、PMS = 3 mmol/L、NOR = 10 mg/L；(b) 阴离子和腐殖酸HA对NOR 降解的影响，反应条件：Mn/P-C =1 g/L、PMS = 3 mmol/L、NOR = 10 mg/L、Cl−=5 mmol/L、CO32-=5 mmol/L、HA=5 mmol/L
Figure 6. (a) Effect of pH for NOR degradation, Reaction conditions: Mn/P-C =1 g/L、PMS = 3 mmol/L、NOR = 10 mg/L; (b) anions and humic acid (HA) for NOR degradation, Reaction conditions: Mn/P-C =1 g/L、PMS = 3 mmol/L、NOR = 10 mg/L、Cl−=5 mmol/L、CO32-=5 mmol/L、HA=5 mmol/L
图 7 Mn/P-C重复使用三次及煅烧恢复后对NOR的去除效果；实验条件： PMS = 3 mmol/L、Mn/P-C = 1 g/L，NOR = 10 mg/L，pH=6
Figure 7. Effect of NOR removal after triple Mn / P-C repeats and recovery from calcination; Experimental conditions: PMS = 3 mmol/L, Mn/P-C = 1 g/L, NOR = 10 mg/L, pH=6
图 8 (a) 以DMPO为捕获剂的Mn/P-C、PMS和Mn/P-C活化PMS体系中SO4•−、•OH、O2•− 的EPR图谱；(b) 以TEMP为捕获剂的Mn/P-C、PMS和Mn/P-C活化PMS体系中1O2 的EPR图谱；实验条件： PMS = 3 mmol/L、Mn/P-C = 1 g/L，NOR = 10 mg/L，pH=6
Figure 8. (a) EPR spectrum of SO4•−、•OH、O2•− radicals in Mn/P-C, PMS and Mn/P-C to activate PMS system with DMPO; (b) EPR spectrum of 1O2 radical in Mn/P-C, PMS and Mn/P-C to activate PMS system with TEMP; Experimental conditions: PMS = 3 mmol/L, Mn/P-C = 1 g/L, NOR = 10 mg/L, pH=6
图 9 (a)不同抑制剂EtOH、TBA、L-histine和p-BQ对NOR的降解动力学；(b)相应的反应速率常数。反应条件：PMS = 3 mmol/L，Mn/P-C = 1 g/L，NOR = 10 mg/L，pH=6
Figure 9. (a) Degradation kinetics of NOR by different scavengers EtOH , TBA , L-histidine and p-BQ；(b)The corresponding degradation reaction rate constants.Reaction conditions:PMS = 3 mmol/L, Mn/P-C = 1 g/L, NOR = 10 mg/L, pH=6
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