RhO2 Modified BiVO4 Thin Film Photoanodes: Preparation and Photoelectrocatalytic Water Splitting Performance

doi:10.15541/jim20210798

Abstract

Abstract:

Bismuth vanadate is one of the most promising photoanodes for photoelectrocatalytic water splitting, however, its photoelectrocatalytic efficiency is still not ideal due to its sluggish kinetic reaction rate. The RhO₂ cocatalyst was loaded on the BiVO₄ thin film photoanode by impregnation method, and the photoelectrochenucal performance of the BiVO₄ photoanode with different RhO₂loadings was studied. RhO₂ with grain size of 10-25 nm was uniformly loaded on the BiVO₄ film with grain size of 100-250 nm and thickness of 400 nm. The BiVO₄photoanode with 1.65% RhO₂ (mass percent) showed the best comprehensive performance, of which the visible-light photocurrent density reached 3.81 mA·cm^-2 under 1.23 V (vs. RHE) in 1.0 mol/L Na₂SO₃ (pH8.5) electrolyte, which was 10.58 times higher than that of bare BiVO₄. In the absence of any sacrificial agent, the photoanodes produced hydrogen and oxygen at the same time at the ratio of close to 2 : 1, and the oxygen production rate was 8.22 µmol/(h·cm²). RhO₂ loading effectively improved the surface water oxidation kinetics, so that photogenerated holes could undergo water oxidation reaction more quickly. Meanwhile, the photogenerated carrier recombination was inhibited, significantly improving the photoelectrocatalytic performance. In addition, since holes were more easily extracted from the surface of photoanode into electrolyte solution in the presence of RhO₂ cocatalyst, reducing accumulation on the surface of the photoanode, the BiVO₄/RhO₂ (1.65%) photoanode achieved excellent stability for more than 10 h.

Key words: BiVO₄, RhO₂, cocatalyst, photoelectrocatalysis, water splitting

CLC Number:

TQ174

HU Yue, AN Lin, HAN Xin, HOU Chengyi, WANG Hongzhi, LI Yaogang, ZHANG Qinghong. RhO₂ Modified BiVO₄ Thin Film Photoanodes: Preparation and Photoelectrocatalytic Water Splitting Performance[J]. Journal of Inorganic Materials, 2022, 37(8): 873-882.

Figures/Tables 10

Fig. 1 (a) XRD patterns and XPS spectra of (b) Bi4f, (c) V2p, (d) Rh3d of all BiVO4/RhO2 photoanodes

Fig. 2 (a, b) Low-magnification and (c, d) high-magnification FESEM images of bare BiVO4 surface and BiVO4/0.1-RhO2 photoanodes, and (e) high-magnification SEM image with elemental mappings of the BiVO4/0.1-RhO2 photoanode

Fig. 3 (a, c) TEM and (b, d) HRTEM images of (a, b) bare BiVO4 and (c, d) BiVO4/0.1-RhO2 photoanodes The inset in (d) is the SAED patterns of the selected area

Fig. 4 (a) UV-Vis DRS spectra and (b) (αhν) 2 vs hν tauc plots of BiVO4/RhO2 photoanodes

Fig. 5 (a) Liner sweep voltammetry curves and (b) photocurrent response plots of BiVO4/RhO2 photoanodes in 1.0 mol/L Na2SO3 (pH8.5) electrolyte

Fig. 6 (a) Liner sweep voltammetry curves and (b) photocurrent response plots of all BiVO4/RhO2 photoanodes in 0.5 mol/L Na2SO4 (pH6.8) electrolyte

Fig. 7 Nyquist plots of the BiVO4/RhO2 photoanodes The inset showing the equivalent circuit

Fig. 8 (a) Photocurrent stability of the BiVO4/0.1-RhO2 photoanode in 1.0 mol/L Na2SO3 (pH8.5) under visible-light illumination, and (b) XRD patterns of the BiVO4/0.1-RhO2 photoanodes before and after illumination, respectively

Fig. 9 (a) Hydrogen and (b) oxygen evolution vs. reaction time per illuminated area for bare BiVO4 and BiVO4/RhO2 photoanodes under visible-light irradiation with the electrolyte of 1.0 mol/L Na2SO3 (pH8.5) as hole scavenger

Fig. 10 Schematic diagram depicting PEC water splitting of the RhO2-modified BiVO4 photoanode under visible light irradiation

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RhO₂ Modified BiVO₄ Thin Film Photoanodes: Preparation and Photoelectrocatalytic Water Splitting Performance

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