Enhanced photocatalytic hydrogen production and simultaneous benzyl alcohol oxidation by modulating the Schottky barrier with nano high-entropy alloys

doi:10.1016/S1872-2067(23)64492-4

Abstract

Abstract:

Catalysts play a vital role in photocatalytic water-splitting by converting solar energy into storable chemical energy. In this study, we successfully synthesized an HCN/HEA heterostructure by rationally combining the Pt₁₈Ni₂₆Fe₁₅Co₁₄Cu₂₇ nano-high-entropy alloy (HEA) as an effective cocatalyst with protonated g-C₃N₄ (HCN) nanosheets, via an electrostatic self-assembly method. The resulting HCN/HEA exhibited remarkable performance in both photocatalytic H₂ production and selective oxidation of benzyl alcohol to benzaldehyde. The integration of HEA into HCN leads to the formation of Schottky junctions, which can significantly accelerate charge migration and reduce the recombination of charge carriers. Further investigations using in situ surface photovoltage imaging demonstrated that the reducing cocatalyst HEA can act as a photogenerated electron trap. The best HCN/HEA heterojunction exhibited excellent photocatalytic hydrogen production activity, reaching 2.4 mmol g^-1 h^-1 and an impressive benzaldehyde production rate of 5.44 mmol g^-1 h^-1. These values were 958 and 6.6 times higher than those achieved with pristine HCN, respectively. This study offers promise for the rational design of high-performance cocatalysts to improve the transport, separation, and utilization of light-release charge carriers.

Key words: High-entropy alloy, Schottky junction, Photocatalytic H₂ evolution, Benzyl alcohol oxidation, Heterojunction

Lijuan Sun, Weikang Wang, Ping Lu, Qinqin Liu, Lele Wang, Hua Tang. Enhanced photocatalytic hydrogen production and simultaneous benzyl alcohol oxidation by modulating the Schottky barrier with nano high-entropy alloys[J]. Chinese Journal of Catalysis, 2023, 51: 90-100.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64492-4

https://www.cjcatal.com/EN/Y2023/V51/I8/90

Figures/Tables 8

Scheme 1. Schematic illustration for the synthesis procedure of HCN/HEA composites.

Fig. 1. (a,b) TEM images of HH-10. Inset shows the histogram of particle size distributions of HEA NPs. (c) HRTEM image of HH-10. AFM images of HCN (d) and HH-10 (e).

Fig. 2. XPS compositional analysis. Survey XPS spectra of HCN, HEA (a), and HH-10 (b) samples. High-resolution XPS spectra of Pt 4f (c), Fe 2p (d), Co 2p (e), Ni 2p (f), Cu 2p (g), C 1s (h), and N 1s (i).

Fig. 3. UPS spectra of the HCN (a), HH-10 (b), and HEA (c) samples. Possible photocatalytic mechanism of the HCN/HEA Schottky junction before contact (d), after contact (e), and under irradiation (f).

Fig. 4. (a) Comparison of photocatalytic activities of HCN, HEA, and HH-x samples in the photocatalytic conversion of 10% BA to H2 and BAD. (b) AQY of HH-10 sample. (c) Comparison of the photocatalytic conversion of BA to BAD and HER by different metal cocatalysts. (d) Cyclic stability of HH-5 composite sample. Reaction solution: 72 mL of water and 8 ml BA. LED light source: λ = 420 nm, 67.7 mW cm-2.

Fig. 5. Transient photocurrent response (a) and EIS (b) plots of HCN and HH-10 samples. Visible light-driven LSV curves (c) and Tafel slope (d) of HCN, HEA, and HH-10 samples. PL spectra (e) and TR-PL (f) decay spectra of HCN and HH-10 samples. Transient photocurrent density of HCN (g) and HH-10 (h) with/without adding H2O2. (i) SPV spectra of HCN and HH-10.

Fig. 6. AFM topography and KPFM image of the HH-10 sample in dark (a,b) and under 420 nm light illumination (c,d). (e) Height distribution of HEA NPs on HCN NSs surface. (f) Surface potential profiles under dark conditions and 420 nm light illumination (the quantitative values are all relative to the same calibrated probe).

Fig. 7. Proposed reaction mechanism for photooxidation-reduction catalyzed BA conversion coupled with H2 evolution over HCN/HEA heterostructure.

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