Preparation of nickel ferrite loaded fir sawdust biochar to activate peroxymonosulfate for Chloroquine Phosphate degradation
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摘要: 近年来，磷酸氯喹(Chloroquine Phosphate, CQP)作为治疗新冠的特效药得到广泛应用，并且由于其具有优异的抗炎症和抗疟疾能力，在疫情结束后仍发挥着重要作用。磷酸氯喹的大量使用对环境造成严重的潜在危害。将废弃的木屑资源化利用，通过共沉淀-无氧煅烧法制备出具有磁回收能力的铁酸镍负载杉木屑生物炭复合材料(Nickel ferrate loaded biochar, NiFe2O4@BC)，并研究其活化过一硫酸盐(Peroxymonosulfate, PMS)降解CQP的性能。利用多种表征对NiFe2O4@BC复合材料的组成结构、表面官能团和石墨化程度进行分析，相较于未改性的杉木屑生物炭(Fir sawdust biochar, BC)，将具有磁性NiFe2O4的负载在生物炭上，使得复合材料的石墨化程度提高，缺陷活性位点也得到增多，对CQP的去除效果得到巨大提高。主要考察了NiFe2O4@BC投加量、PMS浓度、溶液初始pH、共存无机阴离子与腐殖酸在降解CQP过程中的影响。研究表明，当NiFe2O4@BC投加量为0.5 g/L，PMS浓度为1.0 mmol/L，CQP浓度为10 mg/L的条件下，CQP去除率在120分钟达到89%。在偏酸性或者偏碱的条件下更有利于CQP的降解，腐殖酸(Humic acid, HA)对NiFe2O4@BC活化PMS降解CQP具有促进作用。淬灭实验证实，自由基途径和非自由基途径生成的•OH与1O2主导了NiFe2O4@BC/PMS体系对CQP的降解。在同等条件下，对多种污染物均能达到80%以上的降解效果。此外，NiFe2O4@BC循环使用5次后，活化PMS去除CQP的效率仍能达到74%左右。本研究为废弃杉木屑高效、绿色的资源化利用提供了新策略和借鉴意义。Abstract: In recent years, chloroquine phosphate (CQP) has been widely used as a specific drug for the treatment of COVID-19. Even after the epidemic ended, it still plays an important role because of its anti-inflammatory and anti-malaria capabilities. The widespread use of chloroquine phosphate poses serious potential hazards to the environment. Utilizing waste wood chips as resources, a nickel ferrite loaded biochar composite material (NiFe2O4@BC) with magnetic recovery was prepared by co precipitation anaerobic calcination method, and study the performance of activating peroxymonosulfate (PMS) to degrade CQP. The compositional structure, surface functional groups, and degree of graphitization of the NiFe2O4@BC composite were analyzed using various characterizations. Compared with unmodified fir sawdust biochar (Fir sawdust biochar, BC), the loading of magnetic NiFe2O4 on the biochar resulted in an increase in the degree of graphitization of the composite, and an increase in the number of defective active sites, which led to a tremendous increase in the effectiveness of the removal of CQP. The effects of NiFe2O4@BC dosing, PMS concentration, initial pH of the solution, inorganic anions, and humic acid in the degradation of CQP were mainly investigated. Research shows that when NiFe2O4@BC Under the conditions of 0.5 g/L dosage, 1.0 mmol/L PMS concentration, and 10 mg/L CQP concentration, the CQP removal rate reaches 89% in 120 minutes. The degradation of CQP is more favorable under acidic or alkaline conditions, and humic acid (HA) has a promoting effect on the degradation of CQP by NiFe2O4@BC-activated PMS. Quenching experiments confirm that •OH and 1O2 generated by the radical and non-radical pathways dominated the degradation of CQP by the NiFe2O4@BC/PMS system. Under the same conditions, it can achieve more than 80% degradation effect for many kinds of pollutants. In addition, the efficiency of CQP removal by activated PMS could still reach about 74% after NiFe2O4@BC was recycled 5 times. This study provides new strategies and reference significance for the efficient and green resource utilization of discarded fir sawdust.
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Key words:
- biochar /
- degradation /
- sawdust nickel ferrite /
- chloroquine phosphate /
- peroxymonosulfate /
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图 1 杉木屑生物炭(BC) (a)、NiFe2O4 (b)、NiFe2O4@BC (c)和5次循环后NiFe2O4@BC (d)的的SEM图谱
Figure 1. SEM images of Fir sawdust biochar (BC) (a), NiFe2O4 (b), NiFe2O4@BC (c) and NiFe2O4@BC after 5 cycles of recycling (d).
图 2 BC和NiFe2O4@BC的氮气吸附脱附曲线(a)和孔径分布图(b)
Figure 2. N2 adsorption-desorption isotherms(a) and Pore size distribution(b) of BC and NiFe2O4@BC.
图 3 BC、NiFe2O4、NiFe2O4@BC和5次循环后NiFe2O4@BC的XRD谱图
Figure 3. XRD patterns of BC, NiFe2O4, NiFe2O4@BC and NiFe2O4@BC after 5 cycles of recycling
图 4 BC、NiFe2O4、NiFe2O4@BC和5次循环后NiFe2O4@BC的FT-IR图谱(a)，XPS全谱图(b)，C 1s谱图(c)和N 1s谱图(d).
Figure 4. FT-IR spectra (a)、Full spectrum of XPS spectra(b)、 C 1s spectra(c) and O 1s spectra(d) of BC, NiFe2O4, NiFe2O4@BC and NiFe2O4@BC after 5 cycles of recycling
图 6 NiFe2O4@BC降解CQP前后的磁滞回线
Figure 6. The hysteresis loops of NiFe2O4@BC and NiFe2O4@BC after 5 cycles of recycling
图 7 不同材料吸附(a)和活化PMS (b)去除CQP的性能
Figure 7. Adsorption (a) and degradation via PMS activation (b) by different materials for CQP removal.
图 8 NiFe2O4@BC投加量(a)和PMS浓度(b)对CQP降解的影响
Figure 8. Effect of NiFe2O4@BC dosage (a) and PMS concentrations (b) for CQP degradation
图 9 不同初始pH (a)、阴阳离子和腐殖酸(b)对NiFe2O4@BC活化PMS降解CQP的影响
Figure 9. Effect of initial pH (a), ions and humic acid (b) by NiFe2O4@BC activated PMS for CQP degradation
图 10 不同淬灭剂对NiFe2O4@BC活化PMS降解CQP的影响
Figure 10. Effects of different trapping agents by NiFe2O4@BC activated PMS for CQP degradation
图 11 NiFe2O4@BC活化PMS对不同有机污染物的降解(a)和对CQP的5次循环降解效果(b)
Figure 11. Degradation effect of NiFe2O4@BC activated PMS on different organic pollutants(a) and five cycles of CQP (b)
图 12 NiFe2O4@BC反应前后的Fe 2 p(a)和Ni 2 p(b)轨道图谱、NiFe2O4@BC /PMS体系去除CQP的机制(c)和CQP及其中间产物的发育毒性(d)
Figure 12. Fe 2 p(a) and Ni 2 p(b) spectra before and after NiFe2O4@BC use , Mechanism of CQP removal by NiFe2O4@BC/PMS system(c) and Developmental toxicity of CQP and their intermediate products(d)
图 13 CQP在NiFe2O4@BC活化PMS体系中的降解途径
Figure 13. Degradation pathway of CQP in NiFe2O4@BC activated PMS system
表 1 BC和NiFe2O4@BC比表面积和孔隙结构
Table 1. Specific surface area and pore structure of BC and NiFe2O4@BC
Sample Surface
Area /(m2∙g−1)Pore volume/
(cm3∙g−1)Average pore
diameter/nmBC 5.702 0.008 9.404 NiFe2O4@BC 94.712 0.065 9.539 
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