铈掺杂强化碳纳米管活化过一硫酸盐实验研究

doi:10.11949/0438-1157.20211539

摘要/Abstract

摘要：

采用浸渍-煅烧法制备了高效稳定的CeO₂/CNT复合材料。利用X射线衍射、X射线光电子能谱和Raman光谱等手段对材料结构进行表征，并研究了复合材料活化过一硫酸盐（PMS）对磺胺异唑的降解性能。结果表明，在材料投加量为75 mg·L^-1、PMS投加量为0.3 mmol·L^-1、初始pH为5.36时，30 min降解率可达90%以上，50 min内可完全去除，反应过程符合伪一级反应动力学模型，活化剂使用5次后仍有77%的去除率。电子顺磁共振实验表明，SO₄?^-、?OH和¹O₂均参与了反应，碳纳米管表面缺陷可能与¹O₂的形成有关。CeO₂的掺杂提高了碳纳米管中缺陷碳的含量，同时Ce³⁺/Ce⁴⁺为反应提供了更多活性位点，从而有效提升了碳纳米管活化PMS的性能，为铈基碳纳米管复合材料应用于过硫酸盐高级氧化技术提供了借鉴。

关键词: CeO₂, 碳纳米管, 复合材料, 活化, 过一硫酸盐, 磺胺唑, 降解

Abstract:

Efficient and stable CeO₂/CNT composites were prepared by impregnation-calcination method. The structure of the material was characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy, and the degradation performance of sulfisoxazole(SIZ) by activated peroxymonosulfate(PMS) of the composite was studied. The introduction of CeO₂ increases the defects content of carbon nanotubes, and the Ce³⁺/Ce⁴⁺ provides active sites for the reaction, which effectively improves the performance of carbon nanotube when activating PMS. The catalyst performance was studied by investigating the effects of CeO₂ doping amount, catalysts dosage, PMS dosage and initial pH on the degradation system. The results show that when the dosage of catalysts is 75 mg·L^-1, the dosage of PMS is 0.3 mmol·L^-1 and the initial pH is 5.36, the removal rate of SIZ can reach more than 90% in 30 min and 100% in 50 min, and the reaction process conforms to the pseudo first-order reaction kinetic model. After 5 cycles, the catalyst can still maintain 77% degradation. Electron paramagnetic resonance experiments indicated that SO₄?^-, ?OH and ¹O₂ were produced in the degradation of SIZ. The surface defects of carbon nanotubes may be related to the formation of ¹O₂. At the same time, the direct electron transfer mediated by carbon nanotubes was existed in the system. The cycle of Ce³⁺/Ce⁴⁺ in the system promotes the activation of PMS.

Key words: CeO₂, carbon nanotubes, composites, activation, peroxymonosulfate, sulfisoxazole, degradation

中图分类号:

X 52

韩雪, 高生旺, 王国英, 夏训峰. 铈掺杂强化碳纳米管活化过一硫酸盐实验研究[J]. 化工学报, 2022, 73(4): 1743-1753.

Xue HAN, Shengwang GAO, Guoying WANG, Xunfeng XIA. Research of enhanced carbon nanotubes activated peroxymonosulfate by cerium doping[J]. CIESC Journal, 2022, 73(4): 1743-1753.

图/表 11

图1 不同体系对SIZ的降解效果

Fig.1 Degradation effects of different systems on SIZ

图2 NE-2的TEM图像及EDS元素面扫图

Fig.2 TEM images and elemental mapping of NE-2

图3 材料的结构表征

Fig.3 Structural characterization of materials

表1 CNT和NE-2的结构性质

Table 1 Textural properties of CNT and NE-2

样品

比表面积/

(m²?g^-1)

孔体积/

(cm³?g^-1)

平均孔径/

NE-2

CNT

CeO₂

153.2261

118.9917

56.6373

0.514207

0.447211

0.198476

12.2907

13.2003

11.2545

表2 材料的D带与G带强度比（ID/IG）

Table 2 The ID/IG values of materials

I_D/I_G

NE-1

NE-2

NE-3

NE-4

NE-5

0.91

1.04

0.96

0.84

图4 NE-2的XPS谱图

Fig.4 XPS spectra of NE-2

图5 活化剂投加量对SIZ降解率的影响

Fig.5 Effect of catalyst dosages on the removal rate of SIZ

图6 PMS投加量对SIZ降解的影响

Fig.6 Effect of PMS dosages on the removal rate of SIZ

图7 初始pH对SIZ降解的影响

Fig.7 Effect of initial pH on the removal rate of SIZ

图8 NE-2的稳定性研究

Fig.8 Study on the stability of NE-2

图9 活性物种与活化机理研究

Fig.9 Study on active species and activation mechanism

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