Boost proton transfer in water oxidation by constructing local electric fields on BiVO4 photoanodes

doi:10.1016/S1872-2067(25)64665-1

Abstract

Abstract:

The slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction. A method is proposed to accelerate proton transfer by building up local electric fields. Modifying acetic, ethanedioic and propanetricarboxylic (C₆H₈O₆) ligands on BiVO₄ surface results in a potential difference between BiVO₄ and ligands that generates a local electric field which serves as a driving force for proton transfer. Among the ligands, carrying the strongest electron-withdrawing ability, the modification of C₆H₈O₆ forms the strongest local electric field and leads to the fastest proton transfer and the smallest thermodynamic overpotential. C₆H₈O₆-BiVO₄ exhibits 3.5 times photocurrent density as high as that of pure BiVO₄, which is 3.50 mA cm^-2 at 1.23 V_RHE. The onset potential of C₆H₈O₆-BiVO₄ shifts negatively from 0.70 to 0.38 V_RHE. The mechanism for OER transitions from thermodynamically high energy proton-coupled electron transfer to thermodynamically low energy electron transfer as proton transfer is accelerated.

Key words: Proton transfer, BiVO₄, Oxygen evolution reaction, Local electric field, Photoanodes

Zhixing Guan, Ying Zhang, Fangfang Feng, Zhaohui Li, Yanli Liu, Zifeng Wu, Xingxing Zheng, Xionghui Fu, Yuanming Zhang, Wenbin Liao, Jialu Chen, Hongguang Liu, Yi Zhu, Yongge Wei. Boost proton transfer in water oxidation by constructing local electric fields on BiVO₄ photoanodes[J]. Chinese Journal of Catalysis, 2025, 72: 176-186.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64665-1

https://www.cjcatal.com/EN/Y2025/V72/I5/176

Figures/Tables 6

Fig. 1. (a) Formation of CXHXOX-BiVO4 photoanodes. (b,c) SEM images of pristine BiVO4 photoanodes and C2H4O2-BiVO4 photoanodes. (d) TEM images of C2H4O2-BiVO4 photoanodes. (e) HRTEM image of C2H4O2-BiVO4 photoanodes. XRD pattern (f) and FT-IR spectra (g) of BiVO4 and CXHXOX-BiVO4 photoanodes. (h-l) the corresponding EDS elemental mapping images of C2H4O2-BiVO4 photoanode for Bi, V, C, and O, respectively.

Fig. 2. (a) Photocurrent-potential (J-V) curves. (b) Transient photocurrents. (c) Applied bias photon-to-current efficiencies (ABPEs) under a Xenon lamp at 100 mW/cm2 in a 0.1 mol/L phosphate buffer (pH 7.0). (d) Incident photon-to-current efficiencies (IPCEs) under a two-electrode system in a 0.1 mol/L phosphate buffer solution and the applied bias voltage is 1.23 VRHE. (e) Electrochemical impedance spectra (EIS) measured at 1.23 VRHE. (f) UV/Vis diffuse spectra. Inset: Tauc plots of BiVO4 and CxHxOx-BiVO4. (g) the efficiency of light absorption (ηabs). (h) Charge separation efficiency (ηsep). (i) Surface carrier transfer (ηox) of pristine BiVO4 and CxHxOx-BiVO4 photoanodes.

Fig. 3. (a,c,e) J-V curves of BiVO4 and CxHxOx-BiVO4 photoanodes in 0.1 mol/L phosphate H2O and D2O solutions, respectively. (b,d,f) The KIE values of BiVO4 and CxHxOx-BiVO4 calculated from the photocurrent density ratio in H2O and D2O solutions (KIE = JH2O/JD2O). Raman spectra of C2H4O2-BiVO4 after and before PEC (g), C2H2O4-BiVO4 after and before PEC (h), and C6H8O6-BiVO4 after and before PEC (i).

Fig. 4. (a) Mott-Schottky plots of BiVO4 and CXHXOX-BiVO4 photoanodes measured in a 0.1 mol/L phosphate buffer (pH = 7.0) in the dark. Bi 4f (b), V 2p (c), and O 1s (d) XPS spectra for bare BiVO4 and CXHXOX-BiVO4 photoanodes, respectively.

Fig. 5. Charge density difference analyses on BiVO4 (a), C2H4O2-BiVO4 (b), C2H2O4-BiVO4 (c), C6H8O6-BiVO4 (d), gray and blue colors represent charge depletion and accumulation, respectively. The isosurface value is set as 0.02 e/bohr3. (e) DFT-optimized structures and adsorption energies of H2O at the surfaces of BiVO4 and C6H8O6-BiVO4. (f) Gibbs free energy profiles of OER for BiVO4, C2H4O2-BiVO4, C2H2O4-BiVO4 and C6H8O6-BiVO4.

Scheme 1. Electron-proton transfer pathways during interfacial hole transfer for oxidation of BiVO4 (a), C2H4O2-BiVO4 (b), C2H2O4-BiVO4 (c), and C6H8O6-BiVO4 (d).

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Boost proton transfer in water oxidation by constructing local electric fields on BiVO₄ photoanodes

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