TiO2相结工程促进吡虫啉杀虫剂的界面吸附和催化

doi:10.1016/S1872-2067(25)64929-1

催化学报 ›› 2026, Vol. 84: 359-367.DOI: 10.1016/S1872-2067(25)64929-1

TiO₂相结工程促进吡虫啉杀虫剂的界面吸附和催化

刘梦梦^,¹, 张妍^,¹, 谢禹成^,¹, 潘广学(), 操海群(), 叶盛()

安徽农业大学材料与化学学院, 植物保护学院, 农业光催化实验室, 安徽合肥 230036

收稿日期:2025-08-31 接受日期:2025-10-10 出版日期:2026-05-18 发布日期:2026-04-16
通讯作者: *电子信箱: sye503@ahau.edu.cn/shengye@mail.ustc.edu.cn(叶盛),
panguangxue97@stu.ahau.edu.cn(潘广学),
caohaiqun@ahau.edu.cn(操海群).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22372001);安徽省自然科学基金优青项目(2408085Y008);安徽农业大学高层次人才科研启动基金(rc382108);大学生创新创业培训项目(X202310364221);大学生创新创业培训项目(X202410364364)

TiO₂ phase junction engineering for promoted interfacial adsorption and catalysis of imidacloprid insecticide

Mengmeng Liu^,¹, Yan Zhang^,¹, Yucheng Xie^,¹, Guangxue Pan(), Haiqun Cao(), Sheng Ye()

Agricultural Photocatalysis Laboratory, School of Materials and Chemistry & School of Plant Protection, Anhui Agricultural University, Hefei 230036, Anhui, China

Received:2025-08-31 Accepted:2025-10-10 Online:2026-05-18 Published:2026-04-16
Contact: * E-mail: sye503@ahau.edu.cn/shengye@mail.ustc.edu.cn (S. Ye),
panguangxue97@stu.ahau.edu.cn (G. Pan),
caohaiqun@ahau.edu.cn (H. Cao).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22372001);Anhui Natural Science Foundation for Outstanding Young Scholars(2408085Y008);Starting Fund for Scientific Research of High-Level Talents, Anhui Agricultural University(rc382108);Innovation and Entrepreneurship Training Program for College Students(X202310364221);Innovation and Entrepreneurship Training Program for College Students(X202410364364)

摘要/Abstract

摘要：

吡虫啉(IMI)是现代农业害虫防治中全球销量最佳的杀虫剂之一. 然而, IMI的广泛使用造成了严重的生态破坏和健康危害. 开发高效且可持续的IMI降解技术对于减轻环境污染、保护生态系统完整性和保障公众健康至关重要. 尽管半导体光催化为解决该问题提供了一条有前景的途径, 但目前的研究主要集中在增强电荷分离能力以提高催化活性上, 对催化剂结构、降解选择性和环境安全性之间的相互联系仍知之甚少. 基于此, 本文以TiO₂异相结催化剂为模型, 旨在阐明分子结构与降解选择性之间的关系.

本文构建了一种用于光催化降解IMI的锐钛矿相/金红石相TiO₂(A/R-TiO₂)异相结光催化剂. 通过X射线粉末衍射仪、拉曼光谱仪和高分辨透射电子显微镜(HRTEM)测试证明了A/R-TiO₂异相结的成功制备. HRTEM图像中可以清晰看到锐钛矿相TiO₂ (A-TiO₂)和金红石相TiO₂ (R-TiO₂)材料的界面结构. 时间分辨光致发光光谱测试结果证明, 界面的形成促进了光生载流子的分离和传输. A/R-TiO₂异相结表现出显著增强的光催化降解活性, 其反应速率常数分别是A-TiO₂和R-TiO₂的11.5倍和27.7倍, 且矿化率在12 h光照后达到87.6%, 是A-TiO₂和R-TiO₂的2.9倍和3.7倍. A/R-TiO₂在连续5次反应中保持了稳定的降解效率, 这表明其具有优异的催化耐久性. 自由基捕获实验证实了•OH和e^‒是A/R-TiO₂异相结光催化剂的主要活性物种. 电子顺磁共振谱结果表明, A/R-TiO₂产生的•OH多于A-TiO₂和R-TiO₂, 而•O^2‒的产生相对减少, 这与自由基捕获实验结果相吻合. 高效液相色谱-质谱分析证实A-TiO₂和R-TiO₂的降解液中含有毒产物, 而A/R-TiO₂降解IMI后的降解液则是无毒的. 通过生物测试评估了降解产物对于水蚤和大肠杆菌的毒性影响. 结果表明, 由A/R-TiO₂降解IMI的最终产物对生物体无害. 通过使用ECOSAR模型对IMI及其降解中间产物的生态毒理学特征进行了评估, IMI对水蚤具有明显的急性和慢性毒性, 表明存在潜在的生态风险. 然而, 其降解的中间产物生态毒性有所降低. 上述结果表明, A/R-TiO₂异相结光催化剂不仅实现了高效的IMI降解, 而且显著降低了生态风险. 此外,密度泛函理论计算证明, A/R-TiO₂的界面双位点吸附比A-TiO₂和R-TiO₂的单位点吸附具有更大的吸附能, 且促进了界面电荷转移, 从而提升了光催化降解性能.

综上, 本研究设计的A/R-TiO₂异相结展现出优异的光催化降解污染物性能. 这得益于两相界面促进载流子的高效分离, 以及对IMI分子的双位点强吸附效应, 从而降解成环境友好的最终产物. 本工作建立了污染物分子结构-降解性能-产物毒性之间联系的框架, 为设计高效绿色的光催化体系提供新的思路.

关键词: TiO₂异相结, 电荷分离, 界面吸附, 光催化降解, 吡虫啉

Abstract:

Imidacloprid (IMI) is one of the best-selling insecticides worldwide in modern agricultural pest control. However, the extensive and persistent application of IMI raises concerns regarding ecological disruption and health hazards. Although semiconductor photocatalysis offers a promising remediation pathway, the interplay between catalyst structure, degradation selectivity, and environmental safety remains poorly understood. Herein, we report an anatase/rutile TiO₂ phase junction (A/R-TiO₂) for photocatalytic IMI remediation. The A/R-TiO₂ exhibits 11.5-fold and 27.7-fold higher than those of A-TiO₂ and R-TiO₂ in rate constant, with a high mineralization rate of 87.6%. It is found that toxic intermediates during the degradation process of A-TiO₂ and R-TiO₂ are generated, while the final degradation products of A/R-TiO₂ show non-toxicity, confirmed by high performance liquid chromatography-mass spectrometry analysis and biological assessments. Density functional theory calculations demonstrate that compared with single-site adsorption of IMI on A-TiO₂ and R-TiO₂, the interfacial dual-site adsorption on A/R-TiO₂ strengthens the adsorption energy of IMI, accelerates charge separation, and promotes catalytic degradation. These findings underscore the need to establish a structure-function-toxicity framework that redefines photocatalyst design around both kinetic performance and environmental safety.

Key words: TiO₂ phase junction, Charge separation, Interfacial adsorption, Photocatalytic degradation, Imidacloprid

刘梦梦, 张妍, 谢禹成, 潘广学, 操海群, 叶盛. TiO₂相结工程促进吡虫啉杀虫剂的界面吸附和催化[J]. 催化学报, 2026, 84: 359-367.

Mengmeng Liu, Yan Zhang, Yucheng Xie, Guangxue Pan, Haiqun Cao, Sheng Ye. TiO₂ phase junction engineering for promoted interfacial adsorption and catalysis of imidacloprid insecticide[J]. Chinese Journal of Catalysis, 2026, 84: 359-367.

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图/表 5

Fig. 1. The structural characterization of A/R-TiO2. (a) Schematic illustration for the preparation of A/R-TiO2. SEM image (b), TEM image (c), HRTEM image (d), SAED pattern (e), and HAADF image and EDS mapping (f) of A/R-TiO2.

Fig. 2. XRD profiles (a), high-resolution XPS spectra of Ti 2p (b) and O 1s (c), Raman spectra (d), Ti L-edge spectra (e) and O K-edge spectra (f) of A-TiO2, R-TiO2, and A/R-TiO2.

Fig. 3. Photocurrent curves (a), EIS (b), OCP-derived carrier lifetimes (c), and TRPL spectroscopy (d) of A-TiO2, R-TiO2, and A/R-TiO2. (e) Schematic diagram of transfer direction of photogenerated e- and h+ on A/R-TiO2 interface.

Fig. 4. (a) Adsorption (in dark) and degradation (in light) curves of IMI. (b) The corresponding reaction rate constants of A-TiO2, R-TiO2, and A/R-TiO2. (c) The TOC removal efficiency. (d) Comparison of the photodegradation performance of IMI by A-TiO2, R-TiO2, and A/R-TiO2. (e) Reusability of A/R-TiO2. (f) The inhibition ratio of different trapping for A-TiO2, R-TiO2, and A/R-TiO2. DMPO captured EPR spectra for A-TiO2, R-TiO2 and A/R-TiO2 in water for DMPO-?OH (g) and methanol for DMPO-?O2? (h).

Fig. 5. (a) The degradation pathways of IMI in A-TiO2, R-TiO2 and A/R-TiO2. Calculated the acute toxicity of IMI and its removal intermediates by ECOSAR model (b-d) and chronic toxicity (e). (f) The growth status of Escherichia coli under the conditions of blank, IMI and DS. (g,h) The survival rate of daphnid for 6 d under different conditions. The charge density difference (cyan represents charge accumulation, yellow represents charge loss) (i) and adsorption energy (j) of A-TiO2, R-TiO2 and A/R-TiO2. (k) The mechanism of enhanced catalytic performance for IMI degradation.

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TiO₂相结工程促进吡虫啉杀虫剂的界面吸附和催化

TiO₂ phase junction engineering for promoted interfacial adsorption and catalysis of imidacloprid insecticide

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