Rod-like Bi4O5I2/Bi4O5Br2 step-scheme heterostructure with oxygen vacancies synthesized by calcining the solid solution containing organic group

doi:10.1016/S1872-2067(20)63768-8

Abstract

Abstract:

To improve separation efficiency of the photogenerated electron-hole pairs, constructing a heterojunction is considered to be a promising strategy. However, the fabrication of heterojunction via a facile route to achieve a substantial improvement in photocatalytic performance is still challenging. In this work, a well-designed nanosheet-based rodlike step-scheme (S-scheme) heterojunction Bi₄O₅I₂/Bi₄O₅Br₂ with rich oxygen vacancies (OVs) (Bi₄O₅I₂/Bi₄O₅Br₂-OV) was easily synthesized by calcining BiOAc_0.6Br_0.2I_0.2 (Ac ^- = CH₃COO ^-) precursor. The as-prepared Bi₄O₅I₂/Bi₄O₅Br₂-OV exhibited excellent visible light photocatalytic performance towards antibiotic tetracycline (TC) and dye rhodamine B (RhB) degradation and removal rate reached 90.2% and 97.0% within 120 min, respectively, which was higher than those of Bi₄O₅I₂-OV (56.8% and 71.8%), Bi₄O₅Br₂-OV (47.4% and 68.4%), solid solution BiOAc_0.6Br_0.2I_0.2 (67.0% and 84.0%) and Bi₄O₅I₂/Bi₄O₅Br₂ with poor oxygen vacancies (Bi₄O₅I₂/Bi₄O₅Br₂-P) (30.6% and 40.4%). Owing to the release of heat and generation of reducing carbon during calcining the precursor with Ac ^-, it could not only reduce the generation temperature of Bi-rich bismuth oxyhalides, which thus decreased particle size and increased surface areas, but also introduce surface OVs, which could trap photoelectrons and inhibit the recombination of carriers. In addition, the calcination of single solid solution precursor benefited to the formation of well-alloyed interfaces with larger contact areas between 2D/2D nanosheet-like materials, which facilitates charge carriers transfer at the interfaces. The Bi₄O₅I₂/Bi₄O₅Br₂-OV also shows the desirable removal rate for TC and RhB in actual wastewater or in the presence of some electrolytes. This study provides an effective and simple strategy for designing OVs modified Bi-rich oxyhalides heterojunctions.

Key words: Calcination, Organic group-based solid solution, Phase transformation, Oxygen vacancy, S-scheme heterojunction, Photocatalysis

Xuemei Jia, Zichen Shen, Qiaofeng Han, Huiping Bi. Rod-like Bi₄O₅I₂/Bi₄O₅Br₂ step-scheme heterostructure with oxygen vacancies synthesized by calcining the solid solution containing organic group[J]. Chinese Journal of Catalysis, 2022, 43(2): 288-302.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63768-8

https://www.cjcatal.com/EN/Y2022/V43/I2/288

Figures/Tables 11

Fig. 1. Schematic illustration of the synthetic procedures of Bi4O5I2, Bi4O5Br2, Bi4O5I2/Bi4O5Br2-OV and Bi4O5I2/Bi4O5Br2-P.

Fig. 2. XRD patterns of calcinated products of different precursors (a) and BiOAc0.6I0.2Br0.2at different temperatures (b).

Fig. 3. SEM and TEM images of Bi4O5I2/Bi4O5Br2-P (a,c,e) and Bi4O5I2/Bi4O5Br2-OV (b,d,f); STEM image of Bi4O5I2/Bi4O5Br2-OV and the corresponding EDX elemental mapping of Bi, O, I and Br (g).

Fig. 4. The high-resolution XPS spectra Bi 4f (a) and O 1s (b) of Bi4O5I2/Bi4O5Br2-OV and Bi4O5I2/Bi4O5Br2-P; (c) EPR spectra for the as-obtained samples; (d) The production of •O2- by the as-obtained samples detected by the NBT method under visible light.

Fig. 5. (a) UV-vis diffuse reflectance spectra of the as-prepared samples, and the plots of the (ahv)1/2 vs. photon energy (hv) of Bi4O5Br2-OV and Bi4O5I2-OV (inset); Mott-Schottky plots (b) and valence band XPS spectra (c) of Bi4O5Br2-OV and Bi4O5I2-OV; (d) The energy band structures of the samples before and after calcination.

Fig. 6. Photocatalytic activities (a,c), and the corresponding reaction rate constants kapp (b,d) for the as-obtained photocatalysts for TC (a,b) and RhB (c,d) degradation under visible light (λ > 420 nm), and the insets in (b) and (d) showing the corresponding simulated kinetic curves.

Table 1 Comparison of degradation efficiency (DE) of TC and RhB over different photocatalysts.

Sample	Pollutant (mg/L)	Dosage (g/L)	t (min)	Light source	DE (%)	Ref.
Bi_mO_nBr_z Bi₄O₅Br₂ Bi₄O₅I₂-Bi₅O₇I Bi₇O₉I₃-OVR Bi_xO_yI_z/g-C₃N₄ Bi₄O₅I₂/Bi₄O₅Br₂-OV BiOCl/Bi₂₄O₃₁Cl₁₀ Bi₄O₅I₂-Bi₅O₇I BiOI/BiOAc	20 ^a 30 ^a 10 ^a 20 ^a 10 ^a 20 ^a 10 ^b 10 ^b 5 ^b 10 ^b 10 ^b	1.0 0.6 1.0 0.6 1.0 0.4 1.0 1.0 0.4	120 120 240 40 240 120 40 240 80	400W halogen 1000 W Xe 500 W Xe 300 W Xe 500 W Xe 500 W Xe 500 W Xe 500 W Xe 500 W Xe	98.9 75.0 78.0 70.0 40.0 90.2 98.1 79.0 96.0	[41] [12] [37] [34] [42] This work [43] [37] [44]
Bi₇O₉I₃-OVR Bi₄O₅I₂/Bi₄O₅Br₂-OV		0.4 0.4	60 120	300 W Xe 500W Xe	85.0 97.0	[34] This work

Fig. 7. (a) Effect of initial pH on photocatalytic degradation of TC and RhB on Bi4O5I2/Bi4O5Br2-OV; (b) Point of zero charge of Bi4O5I2/Bi4O5Br2-OV; Effect of (c) water sources and (d) electrolytes on the degradation of TC and RhB on Bi4O5I2/Bi4O5Br2-OV.

Fig. 8. (a) Cycling runs of Bi4O5I2/Bi4O5Br2-OV for the degradation of TC and RhB under visible light (λ > 420 nm) and (b) XRD patterns of fresh and used Bi4O5I2/Bi4O5Br2-OV.

Fig. 9. (a) Influence of different scavengers on the degradation of TC and RhB on Bi4O5I2/Bi4O5Br2-OV heterostructures; (b) Nitro blue tetrazolium (NBT) transformation efficiency and (c) fluorescence spectra of TAOH in Bi4O5I2/Bi4O5Br2-OV photocatalytic system under visible light irradiation; (d-f) Schematic illustration of heterostructure: (d) before contact, (e) after contact in darkness and (f) photogenerated charge carrier transfer process in S-scheme heterojunction under illumination.

Fig. 10. Transient photocurrent response of (a) the as-prepared samples and (b) heterojunction Bi4O5I2/Bi4O5Br2-OV and Bi4O5I2/Bi4O5Br2-P with or without K2S2O8; (c) EIS Nyquist plots of the as-prepared samples and the proposed equivalent circuit (insets); (d) PL spectra of as-prepared Bi4O5I2, Bi4O5Br2 and Bi4O5I2/Bi4O5Br2-OV samples.

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Rod-like Bi₄O₅I₂/Bi₄O₅Br₂ step-scheme heterostructure with oxygen vacancies synthesized by calcining the solid solution containing organic group

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