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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64929-1

https://www.cjcatal.com/EN/Y2026/V84/I5/359

Figures/Tables 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 phase junction engineering for promoted interfacial adsorption and catalysis of imidacloprid insecticide

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