Performance and application of EDTA modified carbon nitride in adsorbing ammonia nitrogen in fish ponds
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摘要:目的
制备对鱼塘氨氮有优良吸附性能的氮化碳。
方法通过热缩聚法将三聚氰胺和碳酸氢钠共热制备得到具有基础吸附能力的氮化碳(s−C3N4)，并采用乙二胺四乙酸二钠(EDTA−2Na)改性得到改性氮化碳(EDTA−s−C3N4)。采用扫描电子显微镜(Scanning electron microscope, SEM)、X射线衍射(X-ray diffraction, XRD)、BET 比表面积、Zeta电位等对材料进行表征。
结果EDTA−s−C3N4的比表面积高达
17.7012 m2/g，表面电势为−19 mV，对鱼塘中氨氮有优良的吸附性能，pH=7.5时氨氮去除率达72%。吸附过程符合准二级动力学，Langmuir等温模型拟合估算的最大吸附容量为24.2131 mg/g。EDTA−s−C3N4经过5次循环再生后对氨氮的去除率仍达60%。毒性评价表明EDTA−s−C3N4对斑马鱼安全无毒。结论EDTA−s−C3N4对鱼塘中氨氮有优良的清除效果，安全无毒，实用性好。
Abstract:ObjectiveTo prepare modified carbon nitride with enhanced performance in adsorbing ammonia nitrogen in fish ponds.
MethodCarbon nitride (s-C3N4) with basic adsorption capacity was prepared by co-heating of melamine and sodium bicarbonate using the thermal condensation method, and then s-C3N4 was further modified by disodium ethylene diamine tetraacetic acid (EDTA-2Na) to obtain modified carbon nitride (EDTA-s-C3N4). Scanning electron microscope (SEM), X-ray diffraction (XRD), BET surface area, and Zeta potential were used to characterize the materials.
ResultThe specific surface area of EDTA-s-C3N4 was as high as
17.7012 m2/g, and the surface potential was −19 mV. It had excellent adsorption performance for ammonia nitrogen in fish ponds with the removal rate of 72% at pH=7.5. The adsorption process conformed to quasi-second-order kinetics, and the maximum adsorption capacity estimated by Langmuir isothermal model fitting was24.2131 mg/g. After five cycles of regeneration, EDTA-s-C3N4 still had a removal rate of 60% for ammonia nitrogen. The toxicity evaluation proved that EDTA-s-C3N4 was safe and non-toxic to zebrafish.ConclusionEDTA-s-C3N4 has good removal effect on ammonia nitrogen in fish ponds. It is safe and non-toxic, and has good practicality.
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Keywords:
- EDTA /
- Carbon nitride /
- Modification /
- Ammonia nitrogen /
- Adsorption
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图 1 g−C3N4、s−C3N4和EDTA−s−C3N4的SEM结果
Figure 1. SEM results of g-C3N4, s-C3N4 and EDTA-s-C3N4
a: g-C3N4; b: s-C3N4; c: EDTA-s-C3N4.
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图 2 EDTA−s−C3N4、s−C3N4和g−C3N4的XRD分析结果
1~3为3处特征峰。
Figure 2. XRD analysis results of EDTA-s-C3N4, s-C3N4 and g-C3N4
1−3 are three characteristic peaks.
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图 3 g−C3N4、s−C3N4和EDTA−s−C3N4的Zeta电位
Figure 3. Zeta potentials of g-C3N4, s-C3N4 and EDTA-s-C3N4
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图 4 不同因素对氨氮去除率的影响
Figure 4. Effects of different factors on ammonia nitrogen removal rate
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图 6 准一级动力学模型(a)和准二级动力学模型(b)
Figure 6. Quasi-first-order kinetic model (a) and quasi-second-order kinetic model (b)
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图 7 Langmuir (a)和Freundlich (b)模型吸附等温线
Figure 7. Adsorption isotherm lines of Langmuir (a) and Freundlich (b) models
表 1 g−C3N4、s−C3N4和EDTA−s−C3N4的比表面积
Table 1 Specific surface areas of g-C3N4, s-C3N4 and EDTA-s-C3N4
样品
Sample比表面积/(m2·g−1)
Specific surface area孔容/(cm3·g−1)
Pore volume孔径/nm
Pore sizeg-C3N4 1.2937 0.0010 2.9996 s-C3N4 12.5674 0.0308 9.8030 EDTA-s-C3N4 17.7012 0.0389 8.7958 
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表 2 毒性试验检测斑马鱼存活数量1)
Table 2 Detection of number of survived zebrafish in toxicity experiment
处理
Treatment24 h 48 h 72 h 96 h 空白对照
Blank control10±0 10±0 10±0 10±0 重铬酸钾
Potassium dichromate6±0.816 1±0.816 0±0 0±0 EDTA-s-C3N4 10±0 10±0 10±0 10±0 1)表中数据为3次重复的平均值±标准差。
1) Data in the table is the mean ± standard deviation of three replicates.
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表 3 动力学拟合参数
Table 3 Kinetic fitting parameters
模型 Model qe/(mg·g−1) K R2 准一级动力学
Quasi-first-order kinetic90.6857 0.8643 0.7857 准二级动力学
Quasi-second-order kinetic18.4842 0.0074 0.9925
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