Mo-doping and CoOx loading over BiVO4 photoanode for enhancing performance of H2O2 synthesis and in-situ organic pollutant degradation

doi:10.1016/S1872-2067(24)60175-0

Abstract

Abstract:

The combination of photoelectrochemical water oxidation hydrogen peroxide (H₂O₂) on the anode and hydrogen evolution on the cathode increase the value of the water splitting process. However, the sluggish water oxidation kinetics and slow carrier transport limit the generation of H₂O₂. In this study, to promote H₂O₂ production, the surface of a Mo doped BiVO₄ photoanode was modified with CoO_x co-catalyst. The resulting CoO_x/Mo-BiVO₄ photoanode generates H₂O₂ at a rate of 0.39 μmol min^-1 cm^-2 with a selectivity of 76.9% at 1.7 V_RHE. The experimental results indicate that CoO_x decorated on Mo-BiVO₄ kinetically favors the H₂O₂ production via reduced band bending, while inhibiting H₂O₂ decomposition. According to density functional theory calculations, the loading of CoO_x enhances the efficiency of the Mo-BiVO₄ photoanode in generating H₂O₂. Moreover, the in-situ generated H₂O₂ through CoO_x/Mo-BiVO₄ was applied to the degradation of tetracycline in aqueous solution, finding that CoO_x/Mo-BiVO₄ exhibits the best performance among the catalysts evaluated. This work demonstrates that the CoO_x co-catalyst can effectively facilitate the water oxidation to H₂O₂, opening a way for its application in situ water remediation.

Key words: Hydrogen peroxide, BiVO₄ photoanode, Co-catalyst, Water oxidation reaction, Tetracycline degradation

Tian Tian, Wanting Wang, Yiping Wang, Kexin Li, Yuanyuan Li, Wensheng Fu, Yong Ding. Mo-doping and CoO_x loading over BiVO₄ photoanode for enhancing performance of H₂O₂ synthesis and in-situ organic pollutant degradation[J]. Chinese Journal of Catalysis, 2024, 67: 176-185.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60175-0

https://www.cjcatal.com/EN/Y2024/V67/I12/176

Figures/Tables 8

Fig. 1. Diagram illustrating the synthesis process of CoOx/Mo-BiVO4.

Fig. 2. SEM image (a), HRTEM image (b), and TEM-EDX elemental mapping images (c-h) of CoOx/Mo-BiVO4.

Fig. 3. XPS survey spectra (a), Bi 4f (b), V 2p (c), and O 1s (d) of the BiVO4-based samples. (e) The percentage of different types oxygen in BiVO4 based photoanodes. (f) Co 2p spectra of CoOx/Mo-BiVO4 photoanode.

Fig. 4. (a) LSV curves of the obtained samples. (b) ABPE curves of different catalysts. (c) H2O2 yield and Faraday efficiency for the H2O2 evolution of BiVO4-based photoanodes. (d) Comparison of PEC H2O2 production rates across different products.

Fig. 5. Nyquist plots at 1.7 VRHE in 1 mol L-1 KHCO3 under AM 1.5G illumination (the inset shows the circuit model) (a), MS curves (b) and schematic (c) of the selective PEC H2O2 production for BiVO4-based photoanodes.

Fig. 6. (a) TRPL decay spectra and (b) EPR spectra of BiVO4-based photoanodes.

Fig. 7. The 2e- pathway for H2O2 generation (black line) and 4e- pathway for O2 production (red line) on BiVO4 (a), Mo-BiVO4 (b), CoOx/Mo-BiVO4 (c). (d) The optimized geometries for BiVO4 and Mo-BiVO4. PDOS for BiVO4 (e) and Mo-BiVO4 (f).

Fig. 8. (a) photoanodic degradation efficiency of TC. (b) The impact of various free radical inhibitors on TC degradation. (c) The proposed degradation pathway for tetracycline.

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Mo-doping and CoO_x loading over BiVO₄ photoanode for enhancing performance of H₂O₂ synthesis and in-situ organic pollutant degradation

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