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

doi:10.13801/j.cnki.fhclxb.20240617.004

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

doi: 10.13801/j.cnki.fhclxb.20240617.004

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)；山西工程科技职业大学横向项目(2023HX021)

详细信息

通讯作者:
李世嘉，博士，讲师，研究方向为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: 53
- PDF下载量: 10
- 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: 2024-06-18
- 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 (202229); Scientific Research Project of Shanxi Vocational University of Engineering Science and Technology from Enterprise(2023HX021)

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(7.10 ns)。电子顺磁共振光谱(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⁺、$\text{SO}_{4}^{-}{\text{•}} $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5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 peroxymonosulfate (PMS) for the degradation of tetracycline hydrochloride (TC), resulting in a 90% degradation rate of TC after 60 min 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 electron paramagnetic resonance (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⁺, $\text{SO}_{4}^{-}{\text{•}} $ and •OH are the active species in the reaction system, and a plausible degradation mechanism was proposed. After five cycles of experiments, the degradation rate decreased slightly, showing good photocatalytic performance. This work provides 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XRD图谱(a)、FTIR图谱(b)和Raman图谱(c)

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

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

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

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图 3 CDs/CeVO₄和CeVO₄的全谱图(a)、O1s (b)、Ce3d (c)和V2p (d)图谱；(e) CDs/CeVO₄的C1s图谱；(f) CeVO₄和CDs/CeVO₄的电子顺磁共振光谱(EPR)图谱

Figure 3. Full survey (a), O1s (b), Ce3d (c) and V2p (d) of CDs/CeVO₄ and CeVO₄; (e) C1s spectra of CDs/CeVO₄; (f) Electron paramagnetic resonance (EPR) spectra of CeVO₄ and CDs/CeVO₄

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

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

α—Absorption coefficient; hν—Photon energy; E_g—Band gap; E_VB—Valence band

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图 5 CDs/CeVO₄和CeVO₄的时间分辨荧光光谱

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

τ_ave—Average fluorescence lifetime

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图 6 (a)不同催化体系在光照和未光照下降解盐酸四环素(TC)效率；(b)不同催化体系反应速率常数k

Figure 6. (a) Efficiency of different catalytic systems on tetracycline hydrochloride (TC) degradation with or without light irradiation; (b) Reaction rate constant k for different catalytic systems

PMS—Peroxymonosulfate; Vis—Visible light; P25—Commercial TiO₂; C₀ and C—Concentrations of TC at time 0 and t, respectively

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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图谱

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

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

Figure 8. Photocurrent responses (a) and the electrochemical impedance spectra (b) 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

EDTA-2Na—Ethylenediaminetetraacetic acid disodium salt; BQ—1, 4-benzoquinone

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图 10 光照下CDs/CeVO₄活化PMS机制

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

VB—Valence band; CB—Conduction band; OVs—Oxygen vacancies; NHE—Normal hydrogen electrode

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表 1 不同碳点含量的复合催化剂活化过一硫酸盐(PMS)降解TC效率

Table 1. Efficiency of composite catalysts with different CDs contents 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

CDs/CeVO₄-8 0.108 0.271 0.059 72

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