High-entropy alloy nanocrystals boosting photocatalytic hydrogen evolution coupled with selective oxidation of cinnamyl alcohol

doi:10.1016/S1872-2067(24)60167-1

Abstract

Abstract:

Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen (H₂) production with controllable organic transformation. Herein, we demonstrate that PtFeNiCoCu high-entropy alloy (HEA) nanocrystals can act as efficient cocatalysts for H₂ evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide (CdS) quantum dots (QDs) with uniform sizes of 4.0 ± 0.5 nm. HEA nanocrystals were prepared via a simple solvothermal approach, and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites. The optimized HEA/CdS sample presented an enhanced photocatalytic H₂ production rate of 7.15 mmol g^-1 h^-1, which was 13 times that of pure CdS QDs. Moreover, a cinnamyl alcohol conversion of 96.2% with cinnamaldehyde selectivity of 99.5% was achieved after photoreaction for 3 h. The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm. From d-band center analysis, Pt atoms in the HEA are the active sites for H₂ evolution, exhibiting higher catalytic activity than pure Pt. Meanwhile, the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity. Moreover, femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS, which is vital for achieving enhanced photocatalytic activity. This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.

Key words: Artificial photosynthesis, d-Band center, Photocatalytic hydrogen evolution, Quantum dots, Value-added organic synthesis

Xianglin Xiang, Bei Cheng, Bicheng Zhu, Chuanjia Jiang, Guijie Liang. High-entropy alloy nanocrystals boosting photocatalytic hydrogen evolution coupled with selective oxidation of cinnamyl alcohol[J]. Chinese Journal of Catalysis, 2025, 68: 326-335.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60167-1

https://www.cjcatal.com/EN/Y2025/V68/I1/326

Figures/Tables 5

Fig. 1. Composition of HEA/CdS composites formed by electrostatic self-assembly of cysteamine-capped CdS QDs and PVP-coated HEA nanocrystals. (a) XRD patterns of HEA, CdS, and HEA/CdS. (b) FT-IR spectra of CdS, HEA, and their respective surface coatings (i.e., cysteamine and PVP). (c) Zeta potential of the materials. (d) Illustration for the formation of HEA/CdS composites via a self-assembly approach.

Fig. 2. Morphology and band structure of HEA/CdS composites. HAADF-STEM images with low- (a) and high (b) magnifications, and TEM (c) and HRTEM (d) images of HEA/CdS. Due to the metallic properties of HEA nanocrystals, they are brighter than CdS QDs in the HADDF STEM images and exhibit higher contrast in the TEM images. (e) UPS spectra and the onset of the HOMO region (EHOMO) of CdS, and the inset is the secondary electron cutoff region (Ecutoff) of CdS. (f) UPS spectra and the EHOMO of HEA, and the inset is the Ecutoff of HEA. (g) Electronic band structure of HEA/CdS.

Fig. 3. Enhanced performance and mechanisms for H2 generation coupled with CALC oxidation over the HEA/CdS photocatalysts. (a) The H2-production rate of x%HEA/CdS (x = 0, 10, 20, 40, 80) and HEA. (b) The time course of H2 and CAL evolution and CALC transformation on 40%HEA/CdS. (c) LSV curves of HEA/CdS and CdS, with the dashed line indicating overpotential measured at -0.2 mA cm-2. The calculated free energy of H atom adsorption (ΔGH*) (d) and d-band centers (e) for Pt, Fe, Co, Ni, and Cu in HEA. (f) The calculated ΔGH* for Pt in HEA and pure Pt.

Fig. 4. Reaction pathway for photocatalytic CALC oxidation over HEA/CdS. The pseudo-color in-situ DRIFTS plots of HEA/CdS under dark (a) and light (b) conditions. The in-situ DRIFTS spectra of HEA/CdS under dark (c) and light conditions (d). (e) The EPR spectra of HEA/CdS dispersed in CALC solution with or without light irradiation. (f) Schematic illustration for the band structure of CdS QDs and the oxidation potentials of H2, CALC, and CAL.

Fig. 5. Investigation of charge transfer kinetics in CdS and HEA/CdS by fs-TA spectroscopy. Pseudo-color fs-TA plots of CdS (a) and HEA/CdS (b) using a 400-nm pump laser, and fs-TA spectra of CdS (c) and HEA/CdS (d) at given delay times. Normalized fs-TA kinetics at 450 nm (e) and schematics of electron quenching for these two materials (f).

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