Facile synthesis of medium-entropy metal sulfides as high-efficiency cocatalysts toward photocatalytic hydrogen production

doi:10.1016/S1872-2067(25)64823-6

Abstract

Abstract:

Facing the dual challenges of environmental pollution and energy crisis, photocatalytic water splitting for hydrogen (H₂) production has emerged as a promising strategy to convert solar energy into storable chemical energy. In this work, the medium-entropy metal sulfides ((FeCoNi)S₂) as cocatalysts are successfully anchored onto protonated g-C₃N₄ nanosheets (HCN NSs) to fabricated (FeCoNi)S₂-HCN composite via a solvothermal method. The photocatalytic hydrogen production rate of (FeCoNi)S₂-HCN composite reaches 2996 μmol·h^-1·g^-1, representing 83.22, 9.16, and 1.34-fold enhancements compared to HCN (36 μmol·h^-1·g^-1), FeS₂-HCN (327 μmol·h^-1·g^-1) and (FeCo)S₂-HCN (2240 μmol·h^-1·g^-1). The apparent quantum efficiency of (FeCoNi)S₂-HCN composite attains 12.29% at λ = 370 nm. Comprehensive characterizations and experimental analyses reveal that the superior photocatalytic performance stems from three synergistic mechanisms: (1) The curled-edge lamellar morphology of HCN nanosheets provides a large specific surface area, which enhances light absorption, facilitates electron transfer, and promotes cocatalyst loading. (2) (FeCoNi)S₂ as cocatalyst expands the light absorption range and capacity, accelerates the separation and transfer of electron-hole pairs, and creates abundant active sites to trap photogenerated carriers for surface hydrogen evolution reactions. (3) The synergistic interactions among multiple metallic elements (Fe, Co and Ni) further enhance surface activity, increase photogenerated carrier density, and reduce charge transport resistance, ultimately optimizing hydrogen production efficiency.

Key words: Medium-entropy, Metal sulfides, Protonated g-C₃N₄ nanosheets, Photocatalytic hydrogen production, Cocatalysts

Yunzhu Zang, Jiali Ren, Shanna An, Jian Tian. Facile synthesis of medium-entropy metal sulfides as high-efficiency cocatalysts toward photocatalytic hydrogen production[J]. Chinese Journal of Catalysis, 2025, 78: 242-251.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64823-6

https://www.cjcatal.com/EN/Y2025/V78/I11/242

Figures/Tables 8

Scheme 1. The synthesis process of HCN (a) and (FeCoNi)S2-HCN composites (b) materials.

Fig. 1. (a) XRD patterns of HCN, FeS2-HCN, (FeCo)S2-HCN and (FeCoNi)S2-HCN composites. Survey (b), C 1s (c), N 1s (d), Fe 2p (e), Co 2p (f), Ni 2p (g), S 2p (h), and O 1s (i) XPS spectra of (FeCoNi)S2-HCN composites.

Fig. 2. SEM images of HCN (a), FeS2-HCN (b), (FeCo)S2-HCN (c), and (FeCoNi)S2-HCN (d). TEM (e-h) and EDS elemental mapping (i) images of the (FeCoNi)S2-HCN composite.

Fig. 3. (a) UV-vis absorption spectra of HCN, FeS2-HCN, (FeCo)S2-HCN, and (FeCoNi)S2-HCN composites. Band gap value (b), Mott-Schottky plot (c), and schematic diagram (d) of the band structure of HCN.

Fig. 4. Steady-state (a) and time-resolved (b) PL spectra of HCN and (FeCoNi)S2-HCN composites. Transient photocurrent responses (c) and EIS spectra (d) of HCN, FeS2-HCN, (FeCo)S2-HCN, and (FeCoNi)S2-HCN composites.

Fig. 5. Photocatalytic hydrogen evolution activity (a) and corresponding rates (b) of HCN, FeS2-HCN, (FeCo)S2-HCN, and (FeCoNi)S2-HCN composites. (c) Hydrogen evolution rates for (FeCoNi)S2-HCN in this work compared with representative reported photocatalysts.

Fig. 6. Structural model (a), differential charge density (b), and Gibbs free energy (c) in HER of (FeCoNi)S2-HCN. (d) Schematic illustration of the photocatalytic hydrogen evolution mechanism for the (FeCoNi)S2-HCN composite.

Fig. 7. Structural model of (FeCoNi)S2-HCN (a), (FeCo)S2-HCN (b), FeS2-HCN (c) and HCN (d).

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