Rational design of efficient visible-light photocatalysts (1D@2D/0D) ZnO@Ni-doped BiOBr/Bi heterojunction: Considerations on hierarchical structures, doping and SPR effect

doi:10.1016/j.jmst.2022.01.034

Abstract

Abstract:

Simultaneously integrating heterogeneous interface, element doping, and metal decorating was a promising strategy to promote the visible-light-driven photocatalytic activity. Herein, we demonstrated a facile solvothermal route for Ni-doped BiOBr/Bi⁰ with ZnO 3D hierarchical heterojunction (denoted as Z@B/Bi-Ni). The optimal photocatalysts of Z@B/Bi-Ni sample presented a remarkable catalytic performance of high concentrations of tetracycline solution (40 mg/L) than those of the Z@B/Bi, Z@B, BOB and ZnO photocatalysts toward the visible-light-driven degradation. The enhanced photocatalytic mechanism can be proposed as follows: (i) 3D hierarchical heterojunction provided more active sites and accelerated the separation of charge carriers for photocatalytic TC; (ii) formation of oxygen vacancies on the surface over Z@B/Bi-Ni by in-situ reduction of Bi⁰ and Ni doping could serve as the active sites for oxygen activation to adsorb free O₂ and generate more superoxide radicals; (iii) SPR effect of Bi metal were beneficial to carrier separation and also act as the active site to trap O₂ molecules. This work clarified the role of unique morphologies, surface plasmonic resonance (SPR) effect of metal Bi, and Ni doping in Z@B/Bi-Ni, and its photocatalytic reaction mechanism was proposed by a series of experiments, characterization and DFT calculations, arousing a new perspective to design hierarchical heterojunction photocatalysts.

Key words: Hierarchical heterojunction, Oxygen vacancies, Doping Ni, SPR effect, Photocatalysis

Zhouzheng Jin, Jingru Li, Yiming Zhang, Dan Liu, Hui Ding, Bhekie B. Mamba, Alex T. Kuvarega, Jianzhou Gui. Rational design of efficient visible-light photocatalysts (1D@2D/0D) ZnO@Ni-doped BiOBr/Bi heterojunction: Considerations on hierarchical structures, doping and SPR effect[J]. J. Mater. Sci. Technol., 2022, 125: 38-50.

Figures/Tables 14

Scheme 1. Schematic representation for the synthesis of Z@B/Bi-Ni photocatalyst.

Fig. 1. XRD patterns of (a) ZnO and BOB; (b) Z@B, Z@B-Ni, Z@B/Bi and Z@B/Bi-Ni; (c) partial magnified detail of (b); (d) FTIR spectra of as-prepared samples.

Fig. 2. SEM images of (a) ZnO, (b) BOB, (c) Z@B/Bi and (d) Z@B/Bi-Ni.

Fig. 3. (a) TEM images of Z@B/Bi-Ni samples, (b, c) HRTEM image taken at the interface between BiOBr and Bi, and (d-i) HAADF-STEM/EDX mapping images of the Z@B/Bi-Ni sample.

Fig. 4. N2 adsorption-desorption isotherms and specific surface area (inset) of the as-prepared samples.

Fig. 5. High-resolution XPS spectra of (a) Zn 2p, (b) Bi 4f, (c) Br 3d, (d) O 1s and (e) Ni 2p of Z@B/Bi-Ni. (f) EPR spectra of as-prepared samples of Z@B/Bi-Ni.

Fig. 6. UV-Vis DRS of as-prepared samples (a), Tauc plots (αhv)2 of ZnO (b) and (αhv)1/2 of (c) the rest samples.

Fig. 7. (a) Liquid-phase photocatalytic oxidation of TC for as-prepared samples, (b) corresponding kinetic plots of different samples, effects of (c) interfering cations, (d) anions and (e) initial concentration on photocatalytic TC over Z@B/Bi-Ni material and (f) recycling experiments of photocatalytic.

Fig. 8. Photoluminescence spectra of BOB, Z@B, Z@B/Bi and Z@B/Bi-Ni.

Fig. 9. (a) Transient photocurrent response, (b) Electrochemical impedance spectroscopy (EIS) of as-prepared samples, the Mott-Schottky plots of (c) ZnO and (d) BOB.

Fig. 10. Possible degradation pathways of TC over the Z@B/Bi-Ni composite.

Fig. 11. Trapping experiment of active species during the photocatalytic degradation of TC over Z@B/Bi-Ni photocatalyst under visible light irradiation.

Fig. 12. ESR spin-trapping of Z@B, Z@B/Bi and Z@B/Bi-Ni for (a) DMPO-·O2- and (b) DMPO-·OH under visible light for 4 min. O2 adsorption on (c) Z@B and (d) Z@B/Bi-Ni and their electrons density difference images.

Fig. 13. Schematic diagram of TC degradation over Z@B/Bi-Ni under visible light irradiation.

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