Dual-hole extraction strategy promotes photoelectrochemical water splitting of bismuth vanadate photoanode

doi:10.1016/S1872-2067(25)64778-4

Abstract

Abstract:

Elemental doping of BiVO₄ crystal lattices effectively enhances carrier separation, thereby facilitating efficient photoelectrochemical water splitting. However, the positive effect of elementally induced lattice distortions on hole extraction has been neglected. Herein, the crystal lattice of BiVO₄ is distorted by doping with an inexpensive Cs metal; then, CoFe₂O₄ is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode. Benefiting from the above design, the newly prepared CoFe₂O₄-Cs-BiVO₄ photoanode achieved a photocurrent density of 5.66 mA cm^-2 at 1.23 V vs. a reversible hydrogen electrode, indicating a 3.9-fold improvement in photocurrent density. Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO₄ bulk-phase holes to the CoFe₂O₄ layer. Additionally, the coupled CoFe₂O₄ can be used as a hole extraction layer to further enhance the interfacial migration of carriers. The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO₄ bulk phase to the active sites of the oxygen evolution reaction, thereby effectively inhibiting carrier recombination. This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion, thereby opening new avenues for the rational design of photoanodes.

Key words: Bismuth vanadate, Photoelectrochemical water splitting, Lattice distortion, CoFe₂O₄ hole extraction layer, Dual-hole extraction

Hua Yang, Dingyanyan Zhou, Kaige Tian, Lingjiang Kong, Pengfei An, Jing Zhang, Yujin Ji, Youyong Li, Junqing Yan. Dual-hole extraction strategy promotes photoelectrochemical water splitting of bismuth vanadate photoanode[J]. Chinese Journal of Catalysis, 2025, 77: 236-249.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64778-4

https://www.cjcatal.com/EN/Y2025/V77/I10/236

Figures/Tables 7

Fig. 1. (a) Schematic synthesis of a CoFe2O4-Cs-BiVO4 photoanode. (b) XRD patterns of all photoanodes. (c) Magnified view of the region highlighted in inset (b). (d) Raman spectrum of all photoanodes.

Fig. 2. SEM images of BiVO4 (a), Cs-BiVO4 (b), and CoFe2O4-Cs-BiVO4 (c). TEM images of BiVO4 (d), Cs-BiVO4 (e), and CoFe2O4-Cs-BiVO4 (f). Inset in (d-f) the corresponding selective electron diffraction. (g) AC-TEM image of Cs-BiVO4. (h) EDS element mapping (Bi, V, O, Cs, Co, and Fe) of the CoFe2O4-Cs-BiVO4 photoanode.

Fig. 3. (a) XPS spectra of the Cs 3d energy level of CoFe2O4-Cs-BiVO4. (b) XPS spectra of the Co 2p energy level of CoFe2O4-Cs-BiVO4. (c) Bi L3-edge XANES spectra of a Bi-foil, Bi-BiVO4, and Bi-Cs-BiVO4. (d) R-space Bi L3-edge EXAFS spectra of a Bi foil, Bi-BiVO4, and Bi-Cs-BiVO4. (e) V K-edge XANES spectra of a V foil, V-BiVO4, and V-Cs-BiVO4. (f) R-space V K-edge EXAFS spectra of a V foil, V-BiVO4, and V-Cs-BiVO4. (g) WT-EXANES of a Bi-foil. (h) WT-EXANES of Bi-BiVO4. (i) WT-EXANES of Bi-Cs-BiVO4.

Fig. 4. (a) LSV curves of all photoanodes. (b) ABPE curves of all photoanodes. (c) IPCE curves of all photoanodes. (d) Photocurrent density vs. time curves at 1.23 V vs. RHE for all photoanodes. (e) Comparison of the photocurrents of CoFe2O4-Cs-BiVO4 photoanodes and other BiVO4-based photoanodes. (f) UV-vis absorption spectra of all photoanodes. (g) Bulk charge separation efficiency of all photoanodes. (h) Surface charge injection efficiency of all photoanodes.

Fig. 5. (a) Nyquist plots at 1.23 V vs. RHE for all photoanodes. (b) Mott-Schottky plots. (c) ECSA evaluation. (d) LSV curves in a dark state. (e) Tafel plots of all photoanodes. (f) PL spectrum (excitation at 375 nm). (g) Transient photocurrent curves of all photoanodes. (h) Voltage differences (ΔVOC) based on open circuit photovoltage tests. (i) Transfer time of photoinduced charge carriers produced by all photoanodes in a 1.0 mol L-1 borate buffer solution (pH = 9.2).

Fig. 6. (a) Bi 4f XPS spectrum of CoFe2O4-Cs-BiVO4 following a 15-h stability test. (b) V 2p XPS spectrum of CoFe2O4-Cs-BiVO4 following a 15-h stability test. (c) O 1s XPS spectrum of CoFe2O4-Cs-BiVO4 following 15-h stability test. (d) Cs 3d XPS spectrum of CoFe2O4-Cs-BiVO4 following a 15-h stability test. (e) Fe 2p XPS spectrum of CoFe2O4-Cs-BiVO4 following a 15-h stability test. (f) Co 2p XPS spectrum of CoFe2O4-Cs-BiVO4 following a 15-h stability test.

Fig. 7. DOS diagrams of (a) Cs-BiVO4 and (b) CoFe2O4-BiVO4 photoanodes. Charge density difference diagrams of (c) Cs-BiVO4 and (d) CoFe2O4-Cs-BiVO4 photoanodes. Illustrations of the charge transfer process for (e) BiVO4 and (f) CoFe2O4-Cs-BiVO4 photoanodes.

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