Facet-induced reduction directed AgBr/Ag0/TiO2{100} Z-scheme heterojunction for tetracycline removal

doi:10.1016/S1872-2067(25)64756-5

Abstract

Abstract:

Given their unique structure-dependent properties, strategically designing semiconductor-based photocatalysts, which expose highly reactive crystalline facets, is widely used to tune their performance. Herein, AgBr/Ag/TiO₂{100} nanorods Z-scheme heterojunction composites were prepared via hydrothermal and in situ facet-induced reduction. Transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations reveal that the selective exposure of TiO₂{100} facets with abundant oxygen vacancies (O_V) promotes the formation of metallic silver on the interfaces between AgBr and TiO₂{100}. Metallic silver can mediate interfacial charge transfer by facilitating the photogenerated carrier recombination of the conduction band of TiO₂{100} and the valence band of AgBr. As a result, a Z-scheme heterojunction is formed in AgBr/Ag/TiO₂{100}. The AgBr/Ag/TiO₂{100} exhibits faster degradation of tetracycline in aqueous solution compared to pristine AgBr, TiO₂{101}, TiO₂{100} and AgBr/TiO₂{101} p-n heterojunctions. This is attributed to the effect of the Z-scheme heterojunction on prolonging the lifetime of photogenerated carriers, which is confirmed by femtosecond transient absorption spectroscopy. The photocatalytic mechanism and degradation pathways are discussed along with a toxicity assessment of the intermediates. Overall, this work develops a new approach for designing Z-scheme heterojunction photocatalysts via selective facet control of anatase TiO₂.

Key words: Facet-induced reduction, AgBr/Ag0/TiO2{100}, Z-scheme heterostructure, Oxygen vacancy, Photocatalysis, Tetracycline degradation

Xiong Qi, Shi Quanquan, Wang Binli, Baiker Alfons, Li Gao. Facet-induced reduction directed AgBr/Ag⁰/TiO₂{100} Z-scheme heterojunction for tetracycline removal[J]. Chinese Journal of Catalysis, 2025, 75: 164-179.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64756-5

https://www.cjcatal.com/EN/Y2025/V75/I8/164

Figures/Tables 9

Fig. 1. Hydrothermal synthesis of AgBr/Ag/TiO2{100}, and formation of interfacial Ag.

Fig. 2. TEM image of AgBr/Ag/TiO2{100} (a-c), and AgBr/TiO2{101} (d-f). TEM images of the enlarged portions of AgBr/Ag/TiO2{100} (g) and AgBr/TiO2{101} (i). (h) Fast Fourier transform image of AgBr/Ag/TiO2{100}. (j) Element distribution of Ti, O, Ag, and Br.

Fig. 3. XPS spectra of the TiO2{100}, AgBr, ABT-3, and KBT-3 samples: Ti 2p (a), O 1s (b), Ag 3d (c) and Br 3d (d). XRD pattern (e), EPR spectra (f) and FTIR spectra (g) of specific samples. (h) Density of states of Ag3Br3 cluster, Ag3Br3 supported by OV-TiO2{100}, and Ag3Br3 supported by OV-TiO2{101}. Charge density difference analysis for AgBr/OV-TiO2{100} (i) and AgBr/OV-TiO2{101} (j) heterostructure. The isosurface of the electron density difference was plotted at a value of about 0.002 electron ??1, and the blue and yellow isosurfaces represent the electron depletion and accumulation regions, respectively.

Fig. 4. Semiconductor properties of TiO2{100}, TiO2{101}, AgBr, ABT-3, and KBT-3: UV-vis DRS spectra (a), Tauc plots (b), Mott Schottky curves (c) and VB-XPS survey spectra (d). Degradation properties of the above samples: Time degradation curves (e), quasi-second-order reaction kinetics fitting curve (f), and histogram of reaction rate constants (g). Photoelectric properties: transient photocurrent responses (h) and EIS Nyquist plots (i) with inset showing the equivalent circuit used for fitting the experimental data (Rs, solution resistance, Rct, charge transfer resistance and CPE, constant phase element).

Fig. 5. Three-dimensional fs-TAS of KBT-3 (a) and ABT-3 (d) samples. Fs-TAS spectra of KBT-3 (b) and ABT-3 (e) were observed in the ultraviolet-visible light region under 320 nm pump laser excitation. Fs-TA decay kinetics of the KBT-3 (c) and ABT-3 (f) samples probed at 382 nm under 320 nm pump laser excitation.

Fig. 6. (a) Schematic illustration of AgBr/TiO2{101} and AgBr/Ag/TiO2{100} for expressing photoexcited carrier transfer paths. High-resolution Ti 2p (b) and Br 3d (c) XPS spectra of ABT-3 sample tested in darkness and under illumination (30 min). (d) Effects of different scavengers in the TC photodegradation process. TEMPO-h+ adducts (e), DMPO-?O2? adducts (f) and DMPO-?OH adducts (g) over ABT-3 and KBT-3 under dark and visible light irradiation for 5 min.

Fig. 7. Photocatalytic degradation mechanism over AgBr/Ag/TiO2{100} and AgBr/TiO2{101} systems.

Fig. 8. (a) Optimization of the three-dimensional structure of TC. (b) The main positions corresponding to f-, f0, and f+ in TC. (c) Electrostatic potential distributions of TC. (d) Iso-surfaces of f-, f+, f0 and DD of TC, the value for lime is 0.003, while cyan is -0.003. (e) LUMO and HOMO of TC. (f) Calculation of CFF data.

Fig. 9. (a) Photocatalytic degradation pathways of TC. (b) Acute toxicity evolution of TC and its degradation intermediates toward three aquatic organisms using EPI Suite software with the ECOSAR program. (c) Phenotype of representative cat malt grasses cultivated by deionized water, TC solution and degraded TC solution at five days.

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Facet-induced reduction directed AgBr/Ag⁰/TiO₂{100} Z-scheme heterojunction for tetracycline removal

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