纳米零价铁活化过硫酸盐降解新兴污染物咖啡因

doi:10.19965/j.cnki.iwt.2021-0431

摘要/Abstract

摘要：

采用液相还原法制备纳米零价铁（nZVI），通过X射线衍射、扫描电镜-能谱、傅里叶红外光谱及X射线光电子能谱对其进行表征。考察了nZVI活化过硫酸盐（PS）降解咖啡因（CAF）的性能。实验结果表明，当PS为5 mmol/L、nZVI投加量为0.2 g/L时，50 mg/L的CAF可在15 min内降解97.6%；溶液初始pH和腐殖酸（HA）对nZVI/PS体系降解CAF无影响；Cl^-、SO₄ ^2-、H₂PO₄ ^-和NO₃ ^-对CAF的降解呈抑制效果；自由基抑制实验表明体系中存在·OH与SO₄ ^•-，且SO₄ ^•-占主导，nZVI/PS体系可有效降解多种污染物。

关键词: 纳米零价铁, 过硫酸盐, 硫酸根自由基, 咖啡因, 降解

Abstract:

Nano zero⁃valent iron（nZVI），prepared by liquid phase reduction method，was characterized by X-ray diffraction，scanning electron microscope⁃energy dispersive spectrometer，Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Degradation efficiency of caffeine（CAF） by nZVI activated PS was investigated. The results showed that 97.6% of CAF was degraded within 15 minutes when PS concentration was 5 mmol/L and nZVI dosage was 0.2 g/L. The initial pH and HA had no effect on the degradation of caffeine in the nZVI/PS system. Cl^-，SO₄ ^2-，H₂PO₄ ^-，and NO₃ ^- had a negative effect on the degradation of caffeine. The result of free radical suppression experiment showed that ·OH and SO₄ ^•- coexisted in the system，but SO₄ ^•- dominated， nZVI/PS system can effectively degrade a variety of pollutants.

Key words: nano zero?valent iron, persulfate, sulfate radical, caffeine, degradation

中图分类号:

X703.1

胡明玥, 王玉如, 范家慧, 李敏睿, 饶永芳. 纳米零价铁活化过硫酸盐降解新兴污染物咖啡因[J]. 工业水处理, 2022, 42(1): 100-107.

Mingyue HU, Yuru WANG, Jiahui FAN, Minrui LI, Yongfang RAO. Activation of persulfate by nano zero-valent iron for degradation of emerging pollutant caffeine[J]. Industrial Water Treatment, 2022, 42(1): 100-107.

https://www.iwt.cn/CN/Y2022/V42/I1/100

图/表 13

图1 nZVI的XRD

Fig. 1 XRD pattern of nZVI

图2 nZVI的SEM图及元素分布（a）SEM；（b）电子图像+EDS分层图像；（c）Fe元素分布；（d）O元素分布

Fig. 2 SEM and element mapping of nZVI

表1 nZVI的EDS表面元素含量分析

Table 1 EDS results of elements on nZVI surface

元素	未归一化质量分数/%	归一化质量分数/%	原子分数/%
Fe	79.97	92.41	77.72
O	6.57	7.59	22.28
总计	86.53	100.00	100.00

图3 nZVI的FT-IR

Fig. 3 FT-IR spectra of nZVI

图4 nZVI的XPS全扫描图和Fe 2p谱图（a）XPS全扫描图（b）Fe 2p谱图

Fig. 4 XPS whole scanning spectrum and Fe 2p spectrum of nZVI

图5 不同体系下CAF的降解效能

Fig. 5 Degradation efficiencies of CAF in different systems

图6 不同pH对CAF降解效能的影响

Fig. 6 Effect of pH on the degradation efficience of CAF

图7 nZVI投加量对CAF降解效能的影响和伪一级动力学拟合（a）nZVI投加量对CAF降解效能的影响（b）伪一级动力学拟合

Fig. 7 Degradation efficiencies of CAF and fitting of pseudo⁃first⁃order kinetics under different nZVI dosage

图8 水体常见无机阴离子对CAF降解效能的影响

Fig. 8 Effect of common inorganic anions in water on the degradation efficience of CAF

图9 不同浓度HA对CAF降解效能的影响

Fig. 9 Effect of HA with different concentrations on the degradation efficience of CAF

图10 nZVI/PS/CAF体系与nZVI水体系（pH=2.84）中可溶性铁的浓度变化

Fig. 10 Concentration change of soluble iron in nZVI/PS/CAF and nZVI/water（pH=2.84）

图11 不同浓度TBA与MeOH对咖啡因降解效能的影响

Fig. 11 Effects of TBA and MeOH with different concentrations on the degradation efficience of CAF

图12 NB、NOR、CAP和CAF在不同体系下的降解效能

Fig. 12 Degradation efficiencies of NB，NOR，CAP and CAF in different systems

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