Revealing the dynamics of charge carriers in organic/inorganic hybrid FS-COF/WO3 S-scheme heterojunction for boosted photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(25)64664-X

Abstract

Abstract:

Designing high-efficiency photocatalysts by the construction of organic/inorganic heterojunctions is considered to be an effective approach for improving photocatalytic hydrogen evolution reaction (HER) activity. This work designed and built unique S-scheme heterojunctions by in-situ growing inorganic WO₃ nanoparticles with excellent oxidation ability on fused-sulfone-modified covalent organic frameworks (FS-COF) with strong reduction ability. It is found that FS-COF and WO₃ have a well-matched staggered band alignment. The best-designed FS-COF/WO₃-20% exhibits a maximum photocatalytic HER rate of 24.7 mmol g^-1 h^-1 under visible light irradiation, which is 1.4 times greater than the pure FS-COF. Moreover, photogenerated electron-hole pairs can be separated and utilized more efficiently thanks to the FS-COF/WO₃ heterojunction's ability to create a favorable internal electric field resulting from the difference in work functions between FS-COF and WO₃, which speeds up the transfer dynamics of photoinduced electrons from WO₃ to FS-COF through an additional interfacial electron-transfer channel obeying the directional S-scheme migration mechanism. Furthermore, the S-scheme migration mechanism of photoinduced charge carriers instead of the type-II mechanism was confirmed by the signal intensity of •O₂⁻ species from spin-trapping electron paramagnetic resonance spectra over the single component and the formed heterojunction. It ensures the photoexcited electrons maintain on the lowest unoccupied molecular orbital of FS-COF with a strong reduction ability to participate in photocatalytic HER, resulting in a significantly boosted H₂ evolution rate. Based on organic/inorganic coupling, this work offers a strategy for creating particular S-scheme heterojunction photocatalysts.

Key words: S-scheme heterojunction, Photocatalytic hydrogen evolution, Covalent organic frameworks, Dynamics of charge carriers, Organic/inorganic hybrid

Yunchao Zhang, Jinkang Pan, Xiang Ni, Feiqi Mo, Yuanguo Xu, Pengyu Dong. Revealing the dynamics of charge carriers in organic/inorganic hybrid FS-COF/WO₃ S-scheme heterojunction for boosted photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2025, 74: 250-263.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64664-X

https://www.cjcatal.com/EN/Y2025/V74/I7/250

Figures/Tables 8

Scheme 1. The schematic diagram for the formation of FS-COF/WO3 heterojunction.

Fig. 1. (a) XRD patterns. (b) FTIR spectra. (c) Zeta potentials. N2 adsorption-desorption isotherms tested at -196.15 °C of FS-COF (d), WO3 (e), FS-COF/WO3-20% (f), and pore size distributions (inset).

Fig. 2. (a) XPS survey spectra. The high-resolution C 1s (b), O 1s (c), N 1s (d), S 2p (e), and W 4f (f) XPS spectra.

Fig. 3. SEM images of FS-COF (a), WO3 (b), and FS-COF/WO3-20% (c). TEM images of FS-COF (d) and FS-COF/WO3-20% (e). (f) HRTEM image of FS-COF/WO3-20%. (g) EDS mapping images of FS-COF/WO3-20%.

Fig. 4. (a) Time-dependent H2 generation over prepared samples when exposed to visible light. (b) A bar graph of the photocatalytic H2 production over all as-synthesized samples. (c) The photocatalytic cycling runs over FS-COF/WO3-20%. (d) AQE of FS-COF/WO3-20% at 420, 450, 500, 550, and 600 nm. (e) The water contact angles of prepared samples. (f) UV-Vis DRS spectra and Tauc plots (inset) of samples. (g) Comparison of FS-COF/WO3-20% photocatalytic hydrogen production performance with COF-based heterojunction photocatalytic materials in the literature [20,36,40,43-49].

Fig. 5. (a) EIS Nyquist plots of as-prepared samples. (b) Transient photocurrent response. (c) Mott-Schottky plots of individual components. (d) Energy band-level positions of WO3 and FS-COF.

Fig. 6. (a) Steady-state PL spectra of FS-COF, WO3, and FS-COF/WO3-20% excited by 410 nm. Pseudocolor charts and transient absorption spectra obtained with 340 nm excitation at predetermined delay times: FS-COF (b,d) and FS-COF/WO3-20% (c,e). (f) Decay kinetic curves at 650 nm of FS-COF and FS-COF/WO3-20%.

Fig. 7. The mean electrostatic potentials determined from the surfaces of WO3 (001) (a) and FS-COF (001) (b) at the Z-axis (The corresponding optimized slab structures are displayed in each inset). (c) A constructed geometric model of the FS-COF (001)/WO3 (001) heterojunction interface. (d) Calculated 3D charge density difference distribution of FS-COF (001)/WO3 (001) interface with an isosurface value of 0.0003 e ?-3. The cyan and yellow regions represent electron depletion and accumulation, respectively. (e) DMPO spin-trapping EPR spectra of WO3, FS-COF, and FS-COF/WO3-20%. (f) A diagram showing two possible mechanisms (i.e., Type-II and S-scheme heterojunction) for charge transfer of FS-COF/ WO3-20%. (g) Diagrammatic representation of the charge migration mechanism in the FS-COF/WO3-20% heterostructure both before and after contact under dark and visible light conditions.

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Revealing the dynamics of charge carriers in organic/inorganic hybrid FS-COF/WO₃ S-scheme heterojunction for boosted photocatalytic hydrogen evolution

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