碳点/CeVO<sub>4</sub>纳米复合物协同可见光活化过一硫酸盐降解盐酸四环素

李世嘉; 庞尔楠

碳点/CeVO₄纳米复合物协同可见光活化过一硫酸盐降解盐酸四环素

李世嘉^1, ,,
庞尔楠²

1.
山西工程科技职业大学交通工程学院, 太原 030000
2.
中北大学　材料科学与工程学院, 太原 030051

基金项目: 山西工程科技职业大学校科技创新基金(202229)

详细信息

通讯作者:
李世嘉，博士研究生，讲师，研究方向：高级氧化法降解水中有机污染物　E-mail：lishijia@sxgkd.edu.cn

中图分类号: TB333
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- HTML全文浏览量: 23
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- 被引次数: 0
出版历程
- 收稿日期: 2024-04-29
- 修回日期: 2024-05-27
- 录用日期: 2024-06-08
- 网络出版日期: 2024-06-25
- 刊出日期: 2024-10-15

CDs/CeVO₄ nanohybrids synergistic visible light for activation of peroxymonosulfate toward tetracycline degradation

LI Shijia^{1
, ,},
PANG Ernan²

1.
Institute of Traffic Engineering, Shanxi Vocational University of Engineering Science and Technology, Taiyuan 030000, China
2.
School of Materials Science and Engineering, North University of China, Taiyuan 030051, China

Funds: Science and Technology Innovation Fund of Shanxi Vocational University of Engineering Science and Technology (NO.202229)

摘要

摘要: CeVO₄因其对可见光较低的利用率和光生电子空穴对易于复合的缺点限制其在光催化领域中的应用。碳点(CDs)具有独特的π共轭结构赋予其优异的光生电子存储和转移能力。本研究采用水热和共沉淀两步法成功制备出CDs与CeVO₄的纳米复合物(CDs/CeVO₄)，在掺入CDs后，其光生载流子的转移和分离效率得到有效提高。在可见光照射下，CDs/CeVO₄能高效活化过一硫酸盐(PMS)降解盐酸四环素(TC)，反应60 min后对TC的降解率达到90 %。反应速率常数是CeVO₄的4.1倍(0.03815 min⁻¹)。XPS、紫外可见漫反射光谱和时间分辨荧光光谱测试结果表明，CDs/CeVO₄相比于CeVO₄带隙变窄，可见光吸收能力增强，荧光寿命是CeVO₄的15.1倍(7.1 ns)。EPR与XPS测试结果相互印证掺入CDs的纳米复合物中存在丰富的氧空位，进一步增强其活化PMS能力。活性物质捕获实验表明，h⁺、SO₄^·−和·OH是反应体系中的活性物质,在此基础上提出了该体系可能的降解机制。CDs/CeVO₄表现出良好的稳定性，经过五次循环实验后，仍表现出良好的催化性能。CDs/CeVO₄协同可见光活化PMS降解水中有机污染物为废水治理提供一种新的方法和思路。
- 碳点 /
- 过一硫酸盐(PMS) /
- 光催化 /
- 高级氧化法 /
- 盐酸四环素
Abstract: The limited absorption of visible light and high recombination rate of photogenerated electron-hole pairs impede the practical application of CeVO₄ in photocatalysis. The unique π-conjugated structure of carbon dots(CDs) endows them with exceptional capabilities for the storing and transferring photogenerated electrons. Herein, CDs/CeVO₄ was successfully synthesized by two-step method of hydrothermal and co-precipitation, resulting in a significant enhancement of photogenerated carrier transfer and separation efficiency with the incorporation of CDs. Under visible light irradiation, CDs/CeVO₄ exhibit enhanced activity towards PMS for the degradation of tetracycline hydrochloride(TC), resulting in a 90 % degradation rate of TC after 60 minutes of reaction. The reaction rate constant is 4.1 times higher than that of CeVO₄. XPS, UV-Vis DRS, and time-resolved fluorescence spectra demonstrate that CDs/CeVO₄ exhibits a narrower band gap, an enhanced capacity for absorbing visible light, and a 15.1-fold increase in the fluorescence lifetime compared to CeVO₄. The results of EPR and XPS tests confirm the presence of abundant oxygen vacancies in CDs/CeVO₄, thereby further enhancing their capacity for activating PMS. Capture experiments of active substances show that h⁺、SO₄^·−和·OH are the active species in the reaction system, and a plausible degradation mechanism was proposed. After five cycles of experiments, the degradation rate decrease slightly, showing good photocatalytic performance. This work provide a new strategy for the degradation of organic pollutants in wastewater.
- Carbon dots /
- peroxymonosulfate (PMS) /
- photocatalysis /
- advanced oxidation processes /
- tetracycline

HTML全文

图 1 CeVO₄和碳点(CDs)/ CeVO₄复合催化剂的(a) XRD图谱，(b) FTIR图谱和(c) Raman图谱

Figure 1. (a) XRD patterns, (b) FTIR spectra and (c) Raman spectra of CeVO₄ and carbon dots(CDs)/ CeVO₄ composite catalyst

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图 2 CeVO₄的(a) TEM和(b) HRTEM，CDs/CeVO₄的(c) TEM和(d) HRTEM，(e) CDs/CeVO₄的EDS图

Figure 2. (a) TEM and (b) HRTEM images of CeVO₄. (c) TEM and (d) HRTEM images of CDs/CeVO₄. (e) The EDS images of CDs/CeVO₄

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图 3 XPS谱：CDs/CeVO₄和CeVO₄的(a) 全谱图，(b) O 1s，(c) Ce 3d和(d) V 2p谱图，(e) CDs/CeVO₄的C 1s谱，(f) CeVO₄和CDs/CeVO₄的EPR谱图

Figure 3. XPS spectra: (a) full survey, (b) O 1s, (c) O 1s, (c) Ce 3d and (d) V 2p of CDs/CeVO₄ and CeVO₄. (e) C1s spectra of CDs/CeVO₄. (f) EPR spectra of CeVO₄ and CDs/CeVO₄.

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图 4 CDs/CeVO₄和CeVO₄的(a) 紫外可见漫反射光谱，(b) 相应的Tauc-plot图和(c) VB-XPS图

Figure 4. (a) UV-visible diffuse reflectance spectra of CDs/CeVO₄ and CeVO₄, (b) the corresponding Tauc-plot and (c) VB-XPS

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图 5 CDs/CeVO₄ and CeVO₄的时间分辨荧光光谱

Figure 5. Time-resolved fluorescence spectra of CDs/CeVO₄ and CeVO₄

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图 6 (a) 不同催化体系在光照和未光照下降解TC效率，(b) 不同催化体系反应速率常数

Figure 6. (a) The efficiency of different catalytic systems on TC degradation with or not light irradiation. (b) Reaction rate constants for different catalytic systems

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图 7 (a) CDs/CeVO₄的循环稳定性，(b) 新制备和使用过的CDs/CeVO₄的XRD图

Figure 7. Cyclic stability of CDs/CeVO₄. (b) XRD patterns of new and used CDs/CeVO₄

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图 8 CDs/CeVO₄和CeVO₄的(a)瞬态光电流响应和(b)电化学阻抗图

Figure 8. (a) The photocurrent responses and (b) the electrochemical impedance spectra of CDs/CeVO₄ and CeVO₄

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图 9 加入不同捕获剂对TC降解率的影响

Figure 9. Effect of adding different trapping agents on TC degradation rate

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图 10 光照下CDs/CeVO₄活化PMS机制

Figure 10. The activation PMS mechanism of CDs/CeVO₄ under light irradiation

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表 1 不同碳点含量的复合催化剂活化PMS降解TC效率

Table 1. The efficiency of composite catalysts with different CDs content on TC degradation by activating PMS

Catalyst	CDs/g	Ce(NO₃)₃/g	NH₄VO₃/g	C/C₀/%
CDs/CeVO₄-2	0.027	0.271	0.059	70
CDs/CeVO₄-4	0.054	0.271	0.059	90	this work
CDs/CeVO₄-8	0.108	0.271	0.059	72
Notes：The catalyst (CDs/CeVO₄-4) with the highest degradation rate is used in this work. C₀ and C represent the concentrations of TC at time 0 and t, respectively.

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