S-scheme Cd0.8Zn0.2S nanowires/CeO2 nanocubes heterojunction for efficient photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(25)64843-1

Abstract

Abstract:

Constructing S-scheme heterojunctions preserves the intrinsic redox capabilities of both semiconductors while promoting the separation of photogenerated electrons and holes, making it a promising approach for enhancing the properties of semiconductors. In this study, an S-scheme Cd_0.8Zn_0.2S-CeO₂ (CZS-CeO₂) heterojunction was successfully fabricated via the in-situ growth of CZS nanowires on CeO₂ nanocubes. The S-scheme charge-transfer mechanism of the CZS-CeO₂ composites during photocatalytic reactions was confirmed through in-situ X-ray photoelectron spectroscopy and density functional theory calculations. These results demonstrate that the interfacial electric field (IEF) significantly facilitates charge separation and transport within the heterojunction. Consequently, the CZS-CeO₂ composites exhibited excellent photocatalytic hydrogen production performance under simulated sunlight irradiation, surpassing that of blank CZS. Particularly, the optimal photocatalytic hydrogen generation rate for CZS-15%CeO₂ reached 58 mmol·g^-1·h^-1, approximately 8.8 times higher than that of blank CZS. After five consecutive cycles of testing, CZS-15%CeO₂ retained a relatively high level of activity. This enhanced stability can be attributed to the fabrication of S-scheme heterojunctions, which effectively suppressed hole-induced photocorrosion of CZS. This investigation provides a beneficial reference for the rational design of S-scheme heterojunction photocatalysts for efficient and stable photocatalytic hydrogen production.

Key words: Photocatalytic hydrogen evolution, CeO₂, Cd_0.8Zn_0.2S, S-scheme heterojunction, Built-in electric field

YuQing Yan, YongHui Wu, Jun Wang, JinRong Huo, Kai Yang, KangQiang Lu. S-scheme Cd_0.8Zn_0.2S nanowires/CeO₂ nanocubes heterojunction for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2025, 79: 231-239.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64843-1

https://www.cjcatal.com/EN/Y2025/V79/I12/231

Figures/Tables 6

Fig. 1. (a) Schematic diagram of the preparation of CZS-CeO2 composites. SEM images of CeO2 (b), CZS (c) and CZS-CeO2 composites (d). TEM (e) and HRTEM (f) images of CZS-CeO2 composites. (g) The elemental mapping images of Cd, S, Zn, Ce and O of CZS-CeO2 composites.

Fig. 2. (a) XRD patterns of CZS, CeO2 and CZS-15%CeO2 composites. (b) UV-vis diffuse reflection spectra of CZS, CeO2 and CZS-15%CeO2 composites. Tauc plots of pure CeO2 (c) and CZS (d). Mott-Schottky plots of CeO2 (e) and CZS (f).

Fig. 3. (a) Photocatalytic H2 generation performance of CZS and CZS-CeO2 composites under simulated sunlight irradiation. (b) The photocatalytic H2 evolution stability diagram of the CZS-15%CeO2 composites. (c) A summary of the photocatalytic H2 generation performance of photocatalysts based on CZS and CeO2 reported in recent years. (d) XRD patterns before and after photocatalytic experiment of the CZS-15%CeO2 composites. (e) TEM image after photocatalytic experiment of CZS-15%CeO2. Notably, the error value represents the standard deviation value of photocatalytic activity derived from three repeated tests.

Fig. 4. Linear scanning voltammetry curves (a) and the Tafel slope plots (b) of CZS and CZS-15%CeO2. Photocurrent diagrams (c), electrochemical impedance diagrams (d), PL spectra (e) and plots of capacitance current versus scan rate measured (f) of CeO2, CZS and CZS-15%CeO2.

Fig. 5. High-resolution XPS spectra of Ce 3d (a), O 1s (b), Cd 3d (c), Zn 2p (d) and S 2p (e) in the sample. (f) The bader charge calculation of CZS-CeO2. The calculated electrostatic potential of CZS (002) (g) and CeO2 (111) (h) crystal planes. (i) The differential charge density mapping for CZS-CeO2 heterojunction.

Fig. 6. Schematic of the S-scheme charge transfer process and photocatalytic hydrogen production mechanism of CZS-CeO2 heterojunctions.

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S-scheme Cd_0.8Zn_0.2S nanowires/CeO₂ nanocubes heterojunction for efficient photocatalytic hydrogen evolution

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