Metal-F bond induced by surface fluorination promotes photoelectrochemical selective oxidation of CH3OH to HCHO

doi:10.1016/S1872-2067(25)64831-5

Abstract

Abstract:

Photoelectrochemical (PEC) CH₃OH oxidation provides a promising path to HCHO synthesis instead of thermal catalytic method. However, it suffers the low conversion rate and selectivity. Here, surface fluorinated BiVO₄ photoanodes were fabricated by combined immersion method and PEC treatment for selective CH₃OH oxidation into HCHO. The surface fluorination simultaneously improved the reaction kinetics and selectivity for HCHO synthesis on BiVO₄ photoanode, where the formation of metal‒F bonds promoted the CH₃OH molecules adsorption, O‒H bond stretching, C‒H bond activation, and eventually HCHO desorption, resulting in excellent HCHO production with high selectivity. The optimal photoanode BVO-F2 obtained a photocurrent density of 3.24 mA cm^-2 at 1.2 V_RHE, which is about twice that of the bulk BVO photoanode (1.66 mA cm^-2). In addition, at 0.8V_RHE, the Faraday efficiency of BVO-F2 PEC CH₃OH oxidation for HCHO synthesis reached 90.7%, and maintained relatively stable performance in continuous oxidation for 5 h, and finally accumulated 98.12 µmol HCHO. This work illustrates the potential of surface functionalization in PEC conversion of small molecules, as well as in regulating charge dynamics and catalytic reaction thermodynamics.

Key words: BiVO₄ photoanode, Metal?F bond, Photoelectrochemical CH₃OH oxidation, Surface fluorination, C?H activation

Shutao Li, Kewei Zeng, Zixuan Li, Xiangming Li, Fang Chen, Hongwei Huang. Metal-F bond induced by surface fluorination promotes photoelectrochemical selective oxidation of CH₃OH to HCHO[J]. Chinese Journal of Catalysis, 2026, 80: 227-236.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64831-5

https://www.cjcatal.com/EN/Y2026/V80/I1/227

Figures/Tables 6

Fig. 1. (a) Schematic diagram of preparing fluorinated BVO photoanode. (b) XRD patterns of BVO and BVO-F2. SEM (c), TEM (d), mapping (e), HRTEM (f) and HRTEM linear scan (g) images of BVO-F2.

Fig. 2. (a) LSV curves of BVO, BVO-F1, BVO-F2 and BVO-F3. J-t plots of BVO (b) and BVO-F2 (c) measured in Na2SO4/CH3OH electrolyte (pH = 6.0) at different potentials. (d) Faraday efficiency and yield of HCHO from PEC CH3OH oxidation by BVO, BVO-F1, BVO-F2 and BVO-F3. Photocurrent test results of BVO-F2 photoanode at 0.8 VRHE for 5 h (e) and corresponding Hly HCHO production and Faraday efficiency (f). J-t test of 5-cycle CH3OH oxidation with BVO-F2 photoanode (g) and corresponding HCHO production rate and Faraday efficiency (h).

Fig. 3. Electrochemical impedance spectra of BVO (a) and BVO-F2 (b) measured at different potentials (AM 1.5 G 100 mW cm?2). Transient OCVD plots (c) and Lifetimes (d) of photogenerated carriers of BVO and BVO-F2.

Fig. 4. (a) Electron spin resonance spectra of BVO-F2 in different test solutions. (b) Fluorescence spectra of free hydroxyl radicals produced by different photoanodes in different solutions. (c) J-t test of BVO-F2 in Na2SO4/CH3OH solution containing H2O2 and corresponding Faraday efficiency. (d) Faraday efficiency of CH3OH oxidation to HCHO by BVO-F2 under different trapping agents.

Fig. 5. Charge difference and electron transfer of BVO (a) and BVO-F (b) adsorbed CH3OH molecules. (c) The Planar-averaged electron density difference of BVO and BVO-F adsorbed CH3OH molecule in the Z direction. The bond length of Bi?O bond and O?H bond after relaxation of CH3OH molecules adsorbed by BVO (d) and BVO-F (e).

Fig. 6. The process of PEC CH3OH oxidation to HCHO on BVO (a) and BVO-F (b) and the change of Gibbs free energy (c) at each step.

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Metal-F bond induced by surface fluorination promotes photoelectrochemical selective oxidation of CH₃OH to HCHO

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