NaYF4:Yb,Tm复合TiO2/Bi2WO6光催化降解2,4-二氯苯氧乙酸机制及产物毒性评价

doi:10.16085/j.issn.1000-6613.2024-1110

化工进展 ›› 2025, Vol. 44 ›› Issue (9): 5416-5431.DOI: 10.16085/j.issn.1000-6613.2024-1110

• 资源与环境化工 • 上一篇

NaYF₄:Yb,Tm复合TiO₂/Bi₂WO₆光催化降解2,4-二氯苯氧乙酸机制及产物毒性评价

曾金¹^,²(), 高艳¹^,², 王赵鹏¹^,², 谢雨芸¹^,², 刘俊¹^,², 梁旗², 王春英¹^,²()

^1.矿冶环境污染防控江西省重点实验室，江西赣州 341000
^2.江西理工大学资源与环境工程学院，江西赣州 341000

收稿日期:2024-07-10 修回日期:2024-09-08 出版日期:2025-09-25 发布日期:2025-09-30
通讯作者: 王春英
作者简介:曾金（2002—），男，本科生，研究方向为环境工程。E-mail: jinzeng157@163.com。
基金资助:
江西省自然科学基金(20232BAB203040);矿冶环境污染防控江西省重点实验室项目(2023SSY01071)

Degradation mechanism of 2,4-dichlorophenoxyacetic acid by NaYF₄:Yb,Tm composite TiO₂/Bi₂WO₆ photocatalyst and evaluation of products toxicity

ZENG Jin¹^,²(), GAO Yan¹^,², WANG Zhaopeng¹^,², XIE Yuyun¹^,², LIU Jun¹^,², LIANG Qi², WANG Chunying¹^,²()

^1.Jiangxi Province Key Laboratory of Environmental Pollution Prevention and Control in Mining and Metallurgy, Ganzhou 341000, Jiangxi, China
^2.College of Resources and Environmental Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China

Received:2024-07-10 Revised:2024-09-08 Online:2025-09-25 Published:2025-09-30
Contact: WANG Chunying

摘要/Abstract

摘要：

采用一步水热法合成了具有紫外光和蓝光发射的稀土上转换材料NaYF₄:Yb,Tm。采用溶剂/水热法依次将TiO₂和Bi₂WO₆复合在NaYF₄:Yb,Tm上，制备出复合材料NaYF₄:Yb,Tm@TiO₂(P)@Bi₂WO₆。对材料进行一系列表征分析，结果表明复合材料之间具有紧密的包覆结构，复合后的比表面积有所增大，但孔径变小，XRD（X射线衍射）、XPS（X射线光电子能谱仪）等证实了材料中氧空位的存在，PL（光致发光光谱）和UV-Vis DRS（紫外可见漫反射）结果显示TiO₂/Bi₂WO₆对NaYF₄:Yb,Tm上转换发射的蓝紫光有明显吸收。探究了不同催化剂投加量、2,4-D浓度和外界因素对降解反应的影响，结果表明：①复合光催化剂对2,4-D有着优异的降解性能，在模拟太阳光照射下3h内最优降解率达96%以上；②最佳催化剂投加量在1.0g/L；③水中常见阴离子对降解影响较大，阳离子基本没有影响；强酸条件下会促进反应，碱性条件下会明显抑制反应；腐殖酸低浓度下对反应有部分促进作用，但高浓度下抑制作用明显。通过EPR（电子顺磁共振）测试和自由基捕获实验，表明h⁺（光生空穴）是去除污染物2,4-D过程中起主要作用的活性物质。通过GC-MS（气质联谱）、HPLC（高效液相色谱）等手段测定降解中间产物，并推测出两条降解路径。此外，利用T.E.S.T毒性评估软件对降解中间产物进行了详细的毒性评价，结果显示降解后产物的综合毒性显著降低。

关键词: 2,4-二氯苯氧乙酸, 稀土上转换, 机理, 毒性评价, 降解, 催化剂, 自由基

Abstract:

Rare earth upconversion materials NaYF₄:Yb,Tm with UV and blue light emission were synthesized by a one-step hydrothermal method. The composite material NaYF₄:Yb,Tm@TiO₂(P)@Bi₂WO₆ was prepared by sequentially laminating TiO₂ and Bi₂WO₆ onto NaYF₄:Yb,Tm using solvent/hydrothermal method. A series of characterization analyses were carried out on the materials, and the results showed that the composites had a tight cladding structure between them, and the specific surface area of the composite increased, but the pore size became smaller. XRD (X-ray diffraction) and XPS (X-ray photoelectron spectroscopy) confirmed the existence of oxygen vacancies in the materials. PL (photoluminescence spectroscopy) and UV-Vis DRS (UV-Vis diffuse reflectance) results indicated that TiO₂/Bi₂WO₆could significantly absorb the emitting bule-ultraviolet light from NaYF₄:Yb,Tm. The effects of different catalyst dosage, 2,4-D concentration and external factors on the degradation reaction were investigated. The results showed that (a) the composite photocatalyst had excellent degradation performance for 2, 4-D, and the optimal degradation rate reached more than 96% within 3h under simulated sunlight irradiation, (b) the optimal catalyst dosage was at 1.0 g/L, and (c) the common anions in water had a large effect on the degradation and the cations had no effect; the strong acid condition promoted the reaction, the alkaline condition inhibited the reaction, and humic acid had a partially promotional effect on the reaction at a low concentration but inhibited the reaction obviously at a high concentration. The EPR (electron paramagnetic resonance) test and free radical trapping experiments found that h⁺ (photogenerated holes) was the active substance that played a major role in the removal of 2,4-D. The degradation intermediates were determined by GC-MS (gas chromatography mass spectrometry) and HPLC (high performance liquid chromatography), and two degradation pathways were hypothesized. In addition, a detailed toxicity evaluation of the degradation intermediates was carried out using T.E.S.T Toxicity Evaluation Software, and the results showed that the combined toxicity of the degradation products was significantly reduced.

Key words: 2, 4-dichlorophenoxyacetic acid, rare earth upconversion, mechanism, toxicity evaluation, degradation, catalyst, radical

中图分类号:

X703.1

曾金, 高艳, 王赵鹏, 谢雨芸, 刘俊, 梁旗, 王春英. NaYF₄:Yb,Tm复合TiO₂/Bi₂WO₆光催化降解2,4-二氯苯氧乙酸机制及产物毒性评价[J]. 化工进展, 2025, 44(9): 5416-5431.

ZENG Jin, GAO Yan, WANG Zhaopeng, XIE Yuyun, LIU Jun, LIANG Qi, WANG Chunying. Degradation mechanism of 2,4-dichlorophenoxyacetic acid by NaYF₄:Yb,Tm composite TiO₂/Bi₂WO₆ photocatalyst and evaluation of products toxicity[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5416-5431.

图/表 15

图1 NYT、NYT@Ti(P)和NYT@Ti(P)@B的XRD谱图

图2 光催化剂的SEM图和NYT@Ti(P)@B的元素扫描图

表1 NYT@Ti(P)@B中Na、F、Ti、Bi、W元素占比

元素	Na	F	Ti	Bi	W
原子分数/%	4.63	17.57	15.02	10.56	4.54

图3 光催化剂的N2吸附-脱附等温线及BJH孔径分布（内插图）

图4 NYT、NYT@Ti(P)和NYT@Ti(P)@B的FTIR光谱

图5 NYT@Ti(P)@B的XPS谱图

图6 光催化剂的荧光光谱图、UV-Vis DRS图（包括Tauc图）和两者的重叠图

图7 不同体系降解2,4-D实验（反应条件：催化剂投加量1g/L；pH未调；500W氙灯；2,4-D浓度10mg/L）

图8 三元材料NYT@Ti(P)@B催化剂投加量和循环重复实验（反应条件：催化剂投加量1g/L；pH未调；500W氙灯；2,4-D浓度10mg/L）

图9 离子、pH和腐殖酸浓度等外界因素对NYT@Ti(P)@B光催化降解2,4-D的影响

图10 NYT@Ti(P)@B在太阳辐射下的能量传递和污染物降解机理

图11 NYT@Ti(P)@B自由基捕获实验和EPR光谱

图12 2,4-D降解过程的气质联谱和高效液相色谱演变

图13 NYT@Ti(P)@B降解2,4-D的可能途径和降解中间产物毒性预测

表2 NYT@Ti(P)@B模拟太阳光下降解2,4-D可能的产物

序号	名称	分子式	m/z	时间/min
A	2,4-二氯苯氧乙酸（2,4-D）	C₈H₆Cl₂O₃	219	34.6
B	2,4-二氯苯酚（2,4-DCP）	C₆H₄Cl₂O	162	17.1
C	乙醇酸	C₂H₄O₃	76	无
D	对氯苯酚	C₆H₅ClO	128	无
E	对苯酚（HQ）	C₆H₆O₂	110	无
F	对苯醌（BQ）	C₆H₄O₂	108	无
G	反-2-庚烯酸	C₇H₁₂O₂	128	18.1
H	4-甲氧基-4-甲基-1,2-戊二烯	C₇H₁₂O	112	13.3
I	1-亚丁烯环己烷	C₁₀H₁₆	136	10.3

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NaYF₄:Yb,Tm复合TiO₂/Bi₂WO₆光催化降解2,4-二氯苯氧乙酸机制及产物毒性评价

Degradation mechanism of 2,4-dichlorophenoxyacetic acid by NaYF₄:Yb,Tm composite TiO₂/Bi₂WO₆ photocatalyst and evaluation of products toxicity

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