Full-space electric field-mediated charge migration in mixed-valence MIL-88A(Fe)@BiOBr heterostructures for efficient photocatalytic pollutant removal

doi:10.1016/S1872-2067(26)65045-0

Abstract

Abstract:

Metal-organic frameworks (MOFs) offer an ideal platform for constructing heterostructures to catalyze organic pollutant degradation. However, sluggish charge transfer dynamics within the bulk and at interfacial regions limit removal efficiency. Herein, we engineered a full-space electric field in BiOBr-nanosheet-coated mixed-valence MIL-88A(Fe^II/Fe^III) (m-MIL-88A@BiOBr) heterostructures via charge polarization to overcome this limitation. Specifically, this full-space electric field originates from the synergistic interplay of a bulk electric field (BEF) and an interfacial electric field (IEF), collectively driving the directional flow of photogenerated electrons. Simultaneously, mixed-valent Fe^II/Fe^III metalloclusters establish electron-transfer chains, enhancing charge mobility and IEF intensity. The optimized m-MIL-88A@BiOBr-3 catalyst exhibited exceptional photocatalytic degradation rate constant of 0.023 min⁻¹ for carbamazepine (CBZ) removal, surpassing pristine MIL-88A and BiOBr by factors of 6.99 and 2.15, respectively. Notably, m-MIL-88A@BiOBr-3 demonstrates broad environmental applicability, efficiently mineralizing structurally diverse pollutants (tetracycline, azo dyes, etc.). This work provides critical insights for regulating charge transport in MOF-based heterojunctions.

Key words: Metal-organic frameworks, BiOBr, Mixed-valence, Full-space electric field, Organic pollutants

Biao Zhou, Jianwei Chen, Yanan Chong, Keyou Yan. Full-space electric field-mediated charge migration in mixed-valence MIL-88A(Fe)@BiOBr heterostructures for efficient photocatalytic pollutant removal[J]. Chinese Journal of Catalysis, 2026, 86: 338-349.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65045-0

https://www.cjcatal.com/EN/Y2026/V86/I7/338

Figures/Tables 5

Fig. 1. (a) Schematic illustration for the synthetic procedure of m-MIL-88A@BiOBr heterostructures. (b) SEM image of m-MIL-88A. TEM (c) and HAADF-STEM (d) images of m-MIL-88A@BiOBr. HRTEM (e) and the related SAED (f) images of the selected area A1. (g) HRTEM image of the selected area A2. (h) Corresponding elemental mapping of m-MIL-88A@BiOBr.

Fig. 2. XPS spectra of Fe 2p (a), M?ssbauer spectrum (b), UPS spectra of the cutoff region (c), and calculated internal electric field intensity (assuming the intensity of MIL-88A@BiOBr to be “1”) (d) of as-prepared samples. TDOS (e), simulated charge density, and Barder charge analysis (f) of MIL-88A and m-MIL-88A (the cyan and yellow represent regions of electron depletion and accumulation, respectively). Atomic force microscopy images (g,h), KPFM images (i,j), and corresponding line profiles (k,l) of MIL-88A and m-MIL-88A.

Fig. 3. Photocurrent-time response profiles (a), EIS Nyquist impedance plots (b), Time-resolved PL spectra (c), UV-vis DRS spectra (d), and Mott-Schottky plots (e) of as-prepared samples. (f) Schematic energy-band diagram of m-MIL-88A and BiOBr.

Fig. 4. Adsorption kinetics (a), photocatalytic degradation of TC after adsorption in the dark for 30 min (b), the first-order kinetic curves (c) of BiOBr, MIL-88A, m-MIL-88A, MIL-88A@BiOBr and m-MIL-88A@BiOBr. Influence of incident wavelength on the TC removal efficiency (d), the photodegradation performance under different organic pollutants (e), and the reusability experiments (f) of m-MIL-88A@BiOBr. (g) Electronic structure of the optimized HOMO, LUMO and ESP distribution of CBZ, CIP, TC, and RhB molecule.

Fig. 5. (a) Radical trapping experiments of m-MIL-88A@BiOBr. EPR spectra of DMPO-?OH (b) and DMPO-?O2? (c) for m-MIL-88A and m-MIL-88A@BiOBr. In-situ XPS spectra of Fe 2p (d) and Bi 4f (e) under dark or illumination, (f) Full-space electric field-mediated Type II charge transfer mechanism over m-MIL-88A@BiOBr. (g) Molecular structure of CBZ, computed Fukui index (f 0) distribution, and proposed degradation pathways based on reactive site analysis. (h) Natural population analysis charge distribution of CBZ in various electronic states and the corresponding computed f 0 values.

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