Modulation of Fermi level gap and internal electric field over Cs3Bi2Br9@VO-In2O3 S-scheme heterojunction for boosted charge separation and CO2 photoconversion

doi:10.1016/S1872-2067(23)64549-8

Abstract

Abstract:

Modulating the internal electric field (IEF) represents a potential strategy to stimulate the photocatalytic activity of heterojunctions, especially S-scheme photocatalysts. Herein, a Cs₃Bi₂Br₉@V_O-In₂O₃ (CBB@V_O-In₂O₃) S-scheme heterojunction, of which Cs₃Bi₂Br₉ perovskite quantum dots (PQDs) are embedded into mesoporous V_O-In₂O₃ hosts, is rationally designed as a cornerstone for further IEF manipulation. Briefly, by introducing oxygen vacancies (V_O) into the composed reduction semiconductor (mesoporous In₂O₃), an enlarged Fermi level (E_F) gap between CBB and V_O-In₂O₃ is achieved, yielding an intensified IEF over the CBB@V_O-In₂O₃ heterojunction. Such an enhanced IEF affords a much more robust driving force for directional carrier delivery, leading to accelerated carrier transfer of CBB@V_O-In₂O₃ heterojunction. Consequently, the optimized CBB@V_O-In₂O₃ heterojunction features desirable CO₂-to-CO conversion efficiency, and its CO production rate reaches 130.96 μmol g^-1 h^-1. The reaction intermediates and CO₂ photoconversion pathway were unraveled by in-situ diffuse reflectance infrared Fourier transform spectroscopy. Combining with the DFT calculation, it was revealed that oxygen vacancies in V_O-In₂O₃ act as reactive centers, which optimize the coordination modes of the intermediates, thus reducing the activation energy for photocatalytic CO₂ reduction. Our work demonstrates that the IEF modulation of S-scheme-based heterojunction could significantly boost the charge separation and then to drive efficient catalytic reaction, achieving high-efficiency solar fuel production.

Key words: S-Scheme heterojunction, Internal electric field, Oxygen vacancy, V_O-In₂O₃, Cs₃Bi₂Br₉

Zhijie Zhang, Xuesheng Wang, Huiling Tang, Deben Li, Jiayue Xu. Modulation of Fermi level gap and internal electric field over Cs₃Bi₂Br₉@V_O-In₂O₃S-scheme heterojunction for boosted charge separation and CO₂ photoconversion[J]. Chinese Journal of Catalysis, 2023, 55: 227-240.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64549-8

https://www.cjcatal.com/EN/Y2023/V55/I12/227

Figures/Tables 10

Fig. 1. (a) Graphic representation of the synthesis procedure of CBB@VO-In2O3 heterojunction. (b) Fermi level modulation of In2O3 for intensified IEF of CBB@VO-In2O3 heterojunction.

Fig. 2. EPR spectra (a), O 1s XPS spectra (b), UV-vis DRS (c), Tauc curves (d), M-S curves (e), and CB and VB positions (f) of In2O3 and VO-In2O3.

Fig. 3. Electrostatic potentials of In2O3 (a) and VO-In2O3 (c). DOS of In2O3 (b) and VO-In2O3 (d). The side view (e) and planar-averaged (f) electron density difference of the CBB@VO-In2O3 heterojunction.

Fig. 4. SCD (a), SPV (b), and IEF intensity (c) of CBB, CBB@In2O3, and CBB@VO-In2O3. (d) Amplifying IEF intensity between VO-In2O3 and CBB by introducing oxygen vacancies in In2O3.

Fig. 5. (a) XRD patterns of samples. TEM images of CBB PQDs (b) and the CBB@VO-In2O3 heterojunction (c-e). HRTEM image (f) and elemental mapping (g) of CBB@VO-In2O3.

Fig. 6. Photocatalytic production of CO with irradiation time (a) and CO production rate (b) over CBB, In2O3, VO-In2O3, CBB@In2O3, and CBB@VO-In2O3. (c) Production of CO under various conditions. (d) GC-MS analysis of 13CO from 13CO2 isotope experiment. (e) CO production rate over the CBB@VO-In2O3 heterojunctions with different weight ratios. (f) The recycle activity of CBB@VO-In2O3 for CO2 photoreduction. (g) Comparison of CO2 reduction performances of similar photocatalytic systems presented in recent papers.

Fig. 7. (a) Full-scan XPS of CBB, In2O3, VO-In2O3, and CBB@VO-In2O3 heterojunction. In situ XPS of Cs 3d (b), Bi 4f (c), Br 3d (d), In 3d (e), and O 1s (f) in CBB@VO-In2O3.

Fig. 8. Surface potential distribution variations of VO-In2O3 (a,b) and CBB@VO-In2O3 (c,d) in dark and light (ΔCPD = CPDlight - CPDdark). (e) S-scheme carrier separation mechanism of CBB@VO-In2O3 heterojunction under visible light illumination.

Fig. 9. The transient absorption spectra of CBB (a) and experimental decay kinetics (b) monitored under 550 nm. The transient absorption spectra of CBB@VO-In2O3 (c) and experimental decay kinetics (d) fitted under 520 nm.

Fig. 10. (a) In-situ DRIFTS spectra of CBB@VO-In2O3 collected every 10 min under visible light irradiation. (b) Optimized geometric structures of Gibbs free energy (ΔG) calculation of CO2 photoreduction over CBB@VO-In2O3. (c) Calculated ΔG for major steps in CO2 photoreduction over CBB and CBB@VO-In2O3. (d) Illustration of the mechanism for enhanced photocatalytic CO2 reduction performance over the CBB@VO-In2O3 heterojunction.

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Modulation of Fermi level gap and internal electric field over Cs₃Bi₂Br₉@V_O-In₂O₃S-scheme heterojunction for boosted charge separation and CO₂ photoconversion

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