Manganese-nitrogen co-doped rice husk biochar activated peroxydisulfate to degrade acid orange
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摘要: 为了更好地处理水环境中的偶氮染料(酸性橙,AO7)污染问题,以稻壳、尿素和锰盐为原料,通过热解法制备Mn、N共掺杂生物炭复合材料(Mn-N-BC),活化过二硫酸盐(PDS)降解酸性橙(AO7)染料废水。考察了AO7初始浓度、PDS浓度、催化剂投加量、初始pH值等因素对AO7去除率的影响。结果显示:Mn-N-BC/PDS体系对AO7染料具有较高的去除率,在30 min内可达为98.6%,其表观速率常数kobs为0.125 min−1;并且对水环境中的无机阴离子表现出较高的抗性。在3次循环利用后,AO7的去除率仍在75%左右,表明Mn-N-BC对有机污染物的去除具有较高的可重复利用性和稳定性。自由基淬灭研究、XPS分析表明:Mn-N-BC/PDS体系中AO7的降解机制包括自由基途径(•OH、SO4−•)和非自由基途径(O2−•、1O2和电子转移),其中非自由基途径为主要作用。Abstract: In order to better deal with the problem of azo dye (acid orange, AO7) dye pollution in water environment, Mn and N co-doped biochar composites (Mn-N-BC) were prepared by pyrolysis method using rice husk, urea and manganese salt as raw materials, and acid orange (AO7) dye wastewater was degraded by activated peroxydisulfate (PDS). The effects of initial AO7 concentration, PDS concentration, catalyst dosage and initial pH value on the removal rate of AO7 were investigated. The results show that the Mn-N-BC/PDS system has a high removal rate of AO7 dyes, which can reach 98.6% in 30 min, its apparent rate constant kobs is 0.125 min−1; and shows high resistance to inorganic anions in the water environment. After three times of recycling, the removal rate of AO7 is still about 75%, indicating that Mn-N-BC has high reusability and stability in the removal of organic pollutants. Free radical quenching and XPS analysis showed that the degradation mechanism of AO7 in Mn-N-BC/PDS system included free radical pathway (•OH, SO4−•) and non-free radical pathway (O2−•, 1O2 and electron transfer), in which non-free radical pathway was the main role.
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Key words:
- biochar /
- impurity atoms /
- a total of doping /
- persulfate /
- degradation of dye
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1 原始生物炭(BC) (a),N掺杂生物炭复合材料(N-BC) (b),Mn掺杂生物炭复合材料(Mn-BC) (c),Mn、N共掺杂生物炭复合材料(Mn-N-BC)反应前(d)和反应后(e)催化剂的SEM图像;Mn-N-BC反应前(f)和反应后(g)的EDS图谱;Mn-N-BC元素分布图(10 μm)(h)
1. SEM images of original biochar (BC) (a), N doped biochar composites (N-BC) (b), Mn doped biochar composites (Mn-BC) (c), Mn and N co-doped biochar composites (Mn-N-BC) before (d) and after (e) reaction; EDS of Mn-N-BC before (f) and after (g) reaction; Mn-N-BC element distribution diagram (h)
图 4 (a)不同体系催化剂对酸性橙(AO7)去除的影响;(b)准一级动力学拟合;(c)反应速率常数
PDS—Peroxydi-sulfate
Figure 4. (a) Effects of different catalysts on acid orange (AO7) removal; (b) Quasi first order dynamic fitting; (c) Reaction rate constant
kobs—Pseudo first order kinetic constant (min-1); C—Concentration of AO7 after reaction (mg/L); C0—Concentration of AO7 before reaction (mg/L)
图 10 Mn-N-BC/PDS体系在 5-二甲基-1-氧化吡咯琳(DMPO)和4-氨基-2, 2, 6, 6-四甲基喉啶(TEMP)作用下的EPR光谱:(a) DOPO-SO4–•和DOPO-•OH;(b) TEPM-1O2
Figure 10. EPR spectra of the Mn-N-BC/PDS system with 5-dimethyl-1-pyrrolidine oxide (DMPO) and 4-amino-2, 2, 6, 6-tetramethylthroat (TEMP) reaction conditions: (a) DOPO-SO4–• and DOPO-•OH; (b) TEPM-1O2
表 1 不同材料/PDS体系对AO7的降解动力学参数
Table 1. Kinetic parameters of AO7 degradation by different materials/PDS systems
Catalytic material kobs/min–1 R2 N-BC 0.002 0.8710 Mn-BC 0.010 0.8902 Mn-N-BC 0.125 0.9789 Notes: R—Gas constant; kobs—Apparent rate constant. -
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