Bimetallic NixFe2-xP cocatalyst with tunable electronic structure for enhanced photocatalytic benzyl alcohol oxidation coupled with H2 evolution over red phosphorus

doi:10.1016/S1872-2067(24)60236-6

Abstract

Abstract:

Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics, superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition. In this study, a series of bimetallic nickel-iron phosphide (Ni_xFe_2-_xP, where 0 < x < 2) cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus (RP) for the photocatalytic selective oxidation of benzyl alcohol (BA) coupled with hydrogen production. The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H₂ yield. The RP regulated by bimetallic phosphide cocatalysts (Ni_xFe_2-_xP) demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts (Ni₂P and Fe₂P). In particular, the RP regulated by Ni_1.25Fe_0.75P exhibited the best photocatalytic performance. In addition, experimental and theoretical calculations further illustrated that Ni_1.25Fe_0.75P, with the optimized electronic structure, possessed good electrical conductivity and provided strong adsorption and abundant active sites, thereby accelerating electron migration and lowering the reaction energy barrier of RP. This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.

Key words: Bimetallic phosphides cocatalyst, Composition regulation, Red phosphorus, Selective oxidation of benzyl alcohol H₂

Shuang Li, Haili Lin, Xuemei Jia, Xin Jin, Qianlong Wang, Xinyue Li, Shifu Chen, Jing Cao. Bimetallic Ni_xFe_2-_xP cocatalyst with tunable electronic structure for enhanced photocatalytic benzyl alcohol oxidation coupled with H₂ evolution over red phosphorus[J]. Chinese Journal of Catalysis, 2025, 70: 363-377.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60236-6

https://www.cjcatal.com/EN/Y2025/V70/I3/363

Figures/Tables 7

Fig. 1. (a) Synthetic route of NixFe2-xP/RP. SEM images of Ni1.25Fe0.75P (b), RP (c), and 0.77Ni1.25Fe0.75P/RP (d). TEM (e), HRTEM (f), and EDS elemental mapping (g) of 0.77Ni1.25Fe0.75P/RP.

Fig. 2. (a) XRD patterns of 0.77NixFe2-xP/RP. High-resolution XPS spectra of P 2p (b), Ni 2p (c), and Fe 2p (d) for RP, Ni2P, Fe2P, Ni1.25Fe0.75P, and 0.77Ni1.25Fe0.75P/RP. Estimated energy band-gap energies (e) and Mott-Schottky plots (f) of RP. Calculated band structures and density of states (DOS) of RP (g) and Ni1.25Fe0.75P (h).

Fig. 3. Photocatalytic H2 yield activity over time (a) and H2 and BAD yield rate (b) of RP, Ni2P, Fe2P and 0.77NixFe2-xP/RP under visible light irradiation. (c) UV-vis DRS spectrum and activity of 0.77Ni1.25Fe0.75P/RP for photocatalytic splitting of BAD under different incident light. (d) Photocatalytic oxidation of aromatic alcohols to corresponding aromatic aldehydes and H2 evolution over 0.77Ni1.25Fe0.75P/RP. (e) Long-term photoactivity tests over 0.77Ni1.25Fe0.75P/RP. EIS (f), TPC (g), PL (h), and TRPL decay curves (i) of RP and 0.77NixFe2-xP/RP.

Fig. 4. (a) N2 adsorption-desorption isotherms of Ni2P, Fe2P, Ni1.25Fe0.75P, 0.77Ni1.25Fe0.75P/RP, and RP. Adsorption energies of BA on the (b) Ni2P and RP sides of Ni2P/RP, (c) Fe2P and RP sides of Fe2P/RP, and (d) Ni1.25Fe0.75P and RP sides of Ni1.25Fe0.75P/RP.

Fig. 5. (a) Free radical trapping tests of 0.77Ni1.25Fe0.75P/RP. (b, c) DMPO spin-trapping EPR spectra of Ni1.25Fe0.75P, RP, and 0.77Ni1.25Fe0.75P/RP in BA solution with or without light illumination. (d) In situ DRIFTS spectra of BA oxidation over 0.77Ni1.25Fe0.75P/RP. Free energy diagrams of BA oxidation for (e) Ni1.25Fe0.75P, (f) RP, and (g) Ni1.25Fe0.75P/RP.

Fig. 6. In situ XPS high-resolution spectra of (a) Ni 2p, (b) Fe 2p, and (c) P 2p of 0.77Ni1.25Fe0.75P/RP before and after illumination. Calculated work functions and structural models of (d) RP, (e) Ni1.25Fe0.75P, and (f) Ni1.25Fe0.75P/RP. (g) Schematic of Ni1.25Fe0.75P and RP materials before and after contact in the dark and the migration of photoexcited charges in the 0.77Ni1.25Fe0.75P/RP under light irradiation.

Fig. 7. Schematic of photocatalytic BA oxidation coupled with H2 evolution over NixFe2-xP/RP.

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Bimetallic Ni_xFe_2-_xP cocatalyst with tunable electronic structure for enhanced photocatalytic benzyl alcohol oxidation coupled with H₂ evolution over red phosphorus

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