Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function ZnxCd1-xSy/FePS3 S-scheme heterojunction

doi:10.1016/S1872-2067(25)64830-3

Abstract

Abstract:

Photocatalysis is deemed a green approach to sustainable energy conversion with great promise for addressing future energy challenges. However, traditional photocatalytic systems are often inhibited by rapid recombination of photogenerated electron-hole pairs and low light-harvesting efficiency. To overcome these challenges, an S-scheme heterojunction integrating Zn_xCd_1-_xS_y (ZCS) nanocrystals with FePS₃ (FPS) nanosheets was designed to facilitate both photocatalytic hydrogen evolution and the conversion of benzyl alcohol to benzaldehyde (BAD). The obtained ZCS/FPS-15 (ZCSF-15) heterostructure exhibits remarkable visible-light-harvesting enhancement and charge separation efficiency, delivering a hydrogen evolution rate of 73.06 mmol g^-1 h^-1 and a BAD production rate of 46.68 mmol g^-1 h^-1, corresponding to 22.34- and 53.65-fold performance enhancements, respectively, compared with that of bare ZCS. To reveal the charge transfer dynamics and clarify the reaction mechanisms, in-situ diffuse-reflectance Fourier-transform infrared spectroscopy was used to identify key oxidation intermediates, coupled with interfacial charge transfer dynamics probed using in-situ X-ray photoelectron spectroscopy and atomic force microscopy-Kelvin probe force microscopy. This work establishes a dual-function heterojunction model, offering valuable insights into how to design S-scheme heterojunctions for simultaneous green fuel generation and selective organic synthesis.

Key words: S-scheme heterojunction, Photocatalysis, Hydrogen evolution, Solar energy conversion, Chemical valorization

Rundong Chen, Yuhang Zhang, Bingquan Xia, Xianlong Zhou, Yanzhao Zhang, Shantang Liu. Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function Zn_xCd_1-_xS_y/FePS₃ S-scheme heterojunction[J]. Chinese Journal of Catalysis, 2026, 80: 123-134.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64830-3

https://www.cjcatal.com/EN/Y2026/V80/I1/123

Figures/Tables 10

Scheme 1. Process of synthesizing FPS nanosheets, ZCS, and the ZCS/FPS hybrid.

Fig. 1. (a) TEM image of ZCSF-15. (b) HRTEM image of ZCSF-15. (c) HAADF-STEM image of ZCSF-15. (d-h) Elemental mapping images of ZCSF-15.

Fig. 2. XRD patterns (a) and UV-vis DRS spectra (b) for FPS, ZCS, and ZCSF-x hybrids. PL spectra (c), TRPL spectra (d), EIS spectra (e), and transient photocurrent responses (f) of FPS, ZCS, and ZCSF-15.

Fig. 3. Performance tests of photocatalysts: Hydrogen evolution rate (a), BAD production rate (b), and BAD selectivity (c). Cyclability tests of ZCSF-15: hydrogen evolution (d) and BAD production (e). (f) Comparison of hydrogen evolution and BAD production over ZCSF-15 in water and acetonitrile.

Fig. 4. XPS spectra of Fe 2p (a), Cd 3d (b), Zn 2p (c), S 2p (d), and P 2p (e) for ZCSF-15 before and after the reaction. (f) XRD patterns of ZCSF-15 before and after the reaction.

Fig. 5. XPS spectra of Zn 2p (a) and Cd 3d (b) for pristine ZCS under dark conditions and ZCSF-15 under dark/illuminated conditions. (c) Fe 2p3/2 spectra for pristine FPS under dark conditions and ZCSF-15 under dark/illuminated conditions. (d) Differential charge density plot of the ZCSF interface. The blue and yellow regions denote electron accumulation and depletion, respectively.

Fig. 6. KPFM images of ZCS (a), FPS (d), and ZCSF-15 (g) in darkness. KPFM image of ZCS (b), FPS (e), and ZCSF-15 (h) under Xe lamp irradiation. Contact potential differences of ZCS (c), FPS (f), and ZCSF-15 (i) in darkness and under Xe lamp irradiation.

Fig. 7. (a) Schematic of charge transfer mechanism in ZCSF-x S-scheme heterojunctions before contact, after contact, and under illumination. EPR spectra of ?OH radicals (b) and ?O2? radicals (c) for ZCSF-15 and ZCS under light and dark conditions.

Fig. 8. (a) In-situ DRIFTS spectra of ZCSF-15 during photocatalytic H2 production coupled with BA oxidation. (b) Proposed oxidation steps of BA on ZCSF-15. In-situ DRIFTS spectra of ZCSF-15 in the ranges of 1150-1460 cm-1 (c), 1600-1750 cm-1 (d), and 650-760 cm-1 (e). (f) Calculated ΔGH* of ZCS at different sites. (g) Gibbs free energy of BA on FPS at each reaction stage.

Fig. 9. Proposed mechanism of the cooperative photoredox reaction for the production of H2 and BAD over the ZCSF-x S-scheme heterojunction.

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Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function Zn_xCd_1-_xS_y/FePS₃ S-scheme heterojunction

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