BiOBr/ZnMoO4 Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties

doi:10.15541/jim20220192

Abstract

Abstract:

Photocatalysis is widely used for the removal of refractory organic pollutants in water, but the catalytic activity of semiconductor photocatalysts is significantly inhibited due to the high recombination rate of photogenerated electrons and holes. In this study, an S-scheme BiOBr/ZnMoO₄ composite was successfully prepared by a facile solvothermal method. The structure analysis, in-situ XPS, work function test, free radical capture and ESR experiment confirmed that the BiOBr/ZnMoO₄ composite formed an S-scheme heterojunction. The experimental results show that BiOBr/ZnMoO₄ heterojunction with appropriate ZnMoO₄ content can significantly improve the photocatalytic performance of BiOBr. Compared with pure BiOBr and ZnMoO₄, 15% BiOBr/ZnMoO₄ exhibits the best photocatalytic activity under visible light irradiation, and the photocatalytic degradation rate of bisphenol A reaches 85.3% (90 min). The rate constants of photodegradation of ciprofloxacin are 2.6 times that of BiOBr and 484 times that of ZnMoO₄, respectively. This can be attributed to the tight interfacial bonding between BiOBr and ZnMoO₄ and the formation of S-scheme heterojunction, which enables the efficient spatial separation and transfer of photogenerated carriers. This work provides a simple and efficient method for the directional synthesis of Bi-based S-scheme heterojunction photocatalytic materials, and provides a new theory and experimental basis for further understanding of the structure-activity relationship of Bi-based multi-heterojunction photocatalytic materials.

Key words: S-scheme heterojunction, internal electric field, BiOBr, ZnMoO₄, photocatalysis

CLC Number:

O643

MA Xinquan, LI Xibao, CHEN Zhi, FENG Zhijun, HUANG Juntong. BiOBr/ZnMoO₄ Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties[J]. Journal of Inorganic Materials, 2023, 38(1): 62-70.

Figures/Tables 13

Fig. 1 Preparation process of BiOBr/ZnMoO4 composite photocatalyst

Fig. 2 XRD patterns of the samples (a) and corresponding partial enlarged pattern at 2θ=29°-33°(b)

Fig. 3 TEM images (a, b) and HRTEM images (c) and elemental mapping analyses (d-i) of 15% BiOBr/ZnMoO4 samples

Fig. 4 In-situ XPS spectra of 15% BiOBr/ZnMoO4 (a), and corresponding Bi4f (b), O1s (c), Br3d (d), Zn2p (e) and Mo3d (f) high-resolution XPS spectra

Fig. 5 Photodegradation of BPA by different catalysts under visible light irradiation (a) and corresponding first-order kinetic equations (c); CIP photodegradation (b) and corresponding first-order kinetic equations (d); UV spectra of BPA(e) and CIP(f) photodegraded by 15% BiOBr/ZnMoO4

Fig. 6 Work functions of BiOBr (a), ZnMoO4 (b) and 15% BiOBr/ZnMoO4(c)

Fig. 7 Formation of IEF, band bending and photogenerated charge transfer mechanism before and after BiOBr and ZnMoO4 contact

Fig. 8 Radical trapping experiment of 15% BiOBr/ZnMoO4

Fig. 9 S-scheme heterojunction photocatalytic mechanism of BiOBr/ZnMoO4 photocatalyst

Fig. S1 Cycling test (a) of 15% BiOBr/ZnMoO4 degradation of BPA and XRD spectra before and after photocatalytic cycling (b)

Fig. S2 Transient photocurrent response curves (a) and electrochemical impedance spectra (b)

Fig. S3 Mott-Schottky curves of BiOBr (a) and ZnMoO4 (b); UV-Vis DRS of samples (c); Tauc plots of BiOBr and ZnMoO4 (d)

Fig. S4 ESR detection results of 15% BiOBr/ZnMoO4: DMPO-·OH (a) and DMPO-·O2- (b)

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BiOBr/ZnMoO₄ Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties

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