Facet-oriented surface modification for enhancing photocatalytic hydrogen production on Sm2Ti2O5S2 nanosheets

doi:10.1016/S1872-2067(25)64745-0

Abstract

Abstract:

Oxysulfide semiconductors are promising photocatalysts for visible light-driven water splitting. For a widely studied narrow-bandgap Sm₂Ti₂O₅S₂(STOS), limited bulk charge separation and slow surface reaction heavily restrict its photocatalytic performance. Here, well-crystallized STOS oxysulfide nanosheets, synthesized by a flux-assisted solid-state reaction, were proved to show prominent facet-oriented charge transport property, in which photogenerated electrons migrated to {101} planes and holes to {001} planes of each particle. Hydrogen evolution cocatalysts were therefore precisely positioned on the electron-rich facets to boost the water reduction reaction. In particular, in-situ formation of a Pt_shell@Ir_core core-shell structure on the electron-rich {101} facets and an IrO₂ on the hole-accumulated {001} facets greatly assisted the sacrificial photocatalytic H₂ production over STOS, resulting in an apparent quantum yield as high as 35.9% at 420 nm. By using the highly-active STOS as H₂ evolution photocatalyst, a Mo:BiVO₄ as oxygen evolution photocatalyst, and a [Co(bpy)₃]^2+/3+ as redox shuttle, a Z-Scheme overall water splitting system was constructed to achieve a solar-to-hydrogen conversion efficiency of 0.175%. This work not only elucidates the facet-dependent charge transfer mechanism on STOS but also proposes an ideal strategy for enhancing its photocatalytic performance.

Key words: Oxysulfide, Photocatalysis, Anisotropic charge transport, Overall water splitting, Hydrogen production

Zihao Zhang, Jiaming Zhang, Haifeng Wang, Meng Liu, Yao Xu, Kaiwei Liu, Boyang Zhang, Ke Shi, Jifang Zhang, Guijun Ma. Facet-oriented surface modification for enhancing photocatalytic hydrogen production on Sm₂Ti₂O₅S₂ nanosheets[J]. Chinese Journal of Catalysis, 2025, 74: 341-351.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64745-0

https://www.cjcatal.com/EN/Y2025/V74/I7/341

Figures/Tables 6

Fig. 1. (a) Process for synthesizing STOS powder via the flux-assisted SSR method. (b) Crystal lattice structure of STOS. (c) XRD patterns of STOS powder compared with standard JCPDS card. UV-vis DRS (d), SEM image and EDS elemental mapping (e), and SAED image (f) of STOS particles. The scale bars in EDS image is 1 μm. (g) Schematic representation of the band edge positions for STOS.

Fig. 2. (a) HRTEM image of uniformly distributed Pt nanoparticles by M.S. method on STOS particles. SEM images of STOS particles loaded with photodeposited Pt (b), Au (c), Rh (d), MnOx (f), (g) PbO2, and Pt-MnOx (h). (e) Photocatalytic HER activity over the STOS particles loaded with different cocatalysts under visible light irradiation (λ > 420 nm). The precursors for photodeposition of Pt, Au, Rh, MnOx, PbO2, and Pt-MnOx are H2PtCl6, HAuCl4, Na3RhCl6, MnCl2, (CH3COO)2Pb, and H2PtCl6-MnCl2, respectively. The loading amount of each cocatalyst is 2 wt%.

Fig. 3. (a) Dependence of HER activity and Pt loading amount on STOS by photodeposition. (b) Dependence of HER activity and concentration of AA for the 0.01 wt%, 0.1 wt% and 0.5 wt% Pt-loaded STOS. (c) Schematic illustration of surface reactions with low and high Pt loading. HRTEM images of the photodeposited Pt nanoparticles with the loading amount of 0.01 wt% (d), 0.05 wt% (e), 0.1 wt% (f), 0.5 wt% (g), 1 wt% (h) and 1.5 wt% (i). Insets are the distribution of the size of Pt nanoparticles.

Fig. 4. (a) HER activities of STOS loaded with different cocatalysts. (b) XPS analysis of Ir species loaded on STOS. HRTEM images of Ir nanoparticle on Ir/STOS/IrO2 (c) and Pt@Ir core-shell structure on Pt@Ir/STOS/IrO2 (d). (e) Time courses of HER on STOS powder loaded with IrO2 and/or Pt cocatalysts. Prolonged time courses (f) and wavelength dependence (g) of the AQY for HER over the Pt@Ir/STOS/IrO2 powder. The amounts of catalysts are 50 mg for (a), (e) and (f), and 100 mg for (g).

Fig. 5. Schematic illustration, topography 3D images, SPV spectroscopy, and linear distribution of SPV values for bare STOS (a1-a4), Pt(P.D.)/STOS (b1-b4), and Pt@Ir/STOS/IrO2 (c1-c4) nanosheets. The scale bars in a2 (b2,c2) are 1 μm.

Fig. 6. (a) Schematic illustration of the Z-scheme OWS system constructed using CrOx@Pt@Ir/STOS/IrO2 as HEP, RuOx/BVO as OEP, and [Co(bpy)3]3+/2+ as the redox pair. (b) H2/O2 gas evolution rates for the Z-schemes constructed using STOS particles loaded with different cocatalysts as HEP. (c) Time courses of OWS by the Z-scheme irradiated under a 300 W xenon lamp equipped with a cut-off filter (λ > 420 nm). (d) Time course and STH of OWS by the Z-scheme irradiated under an AM 1.5G solar simulator (100 mW cm-2).

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Facet-oriented surface modification for enhancing photocatalytic hydrogen production on Sm₂Ti₂O₅S₂ nanosheets

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