Integration of 2D layered CdS/WO3 S-scheme heterojunctions and metallic Ti3C2 MXene-based Ohmic junctions for effective photocatalytic H2 generation

doi:10.1016/S1872-2067(21)63883-4

Abstract

Abstract:

The rapid recombination of photo-generated electron-hole pairs, insufficient active sites, and strong photocorrosion have considerably restricted the practical application of CdS in photocatalytic fields. Herein, we designed and constructed a 2D/2D/2D layered heterojunction photocatalyst with cascaded 2D coupling interfaces. Experiments using electron spin resonance spectroscopy, ultraviolet photoelectron spectroscopy, and in-situ irradiation X-ray photoelectron spectroscopy were conducted to confirm the 2D layered CdS/WO₃ step-scheme (S-scheme) heterojunctions and CdS/MX ohmic junctions. Impressively, it was found that the strong interfacial electric fields in the S-scheme heterojunction photocatalysts could effectively promote spatially directional charge separation and transport between CdS and WO₃ nanosheets. In addition, 2D Ti₃C₂ MXene nanosheets with a smaller work function and excellent metal conductivity when used as a co-catalyst could build ohmic junctions with CdS nanosheets, thus providing a greater number of electron transfer pathways and hydrogen evolution sites. Results showed that the highest visible-light hydrogen evolution rate of the optimized MX-CdS/WO₃ layered multi-heterostructures could reach as high as 27.5 mmol/g/h, which was 11.0 times higher than that of pure CdS nanosheets. Notably, the apparent quantum efficiency reached 12.0% at 450 nm. It is hoped that this study offers a reliable approach for developing multifunctional photocatalysts by integrating S-scheme and ohmic-junction built-in electric fields and rationally designing a 2D/2D interface for efficient light-to-hydrogen fuel production.

Key words: Photocatalytic hydrogen evolution, 2D layered S-scheme heterojunction, CdS nanosheets, WO₃ nanosheets, Ti₃C₂ MXene-based ohmic junctions, Cascade 2D coupling interfaces

Junxian Bai, Rongchen Shen, Zhimin Jiang, Peng Zhang, Youji Li, Xin Li. Integration of 2D layered CdS/WO₃ S-scheme heterojunctions and metallic Ti₃C₂ MXene-based Ohmic junctions for effective photocatalytic H₂ generation[J]. Chinese Journal of Catalysis, 2022, 43(2): 359-369.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63883-4

https://www.cjcatal.com/EN/Y2022/V43/I2/359

Figures/Tables 11

Scheme 1. Schematic of the fabrication of MX-CdS/WO3 composites.

Fig. 1. (a) The XRD patterns of CdS, CdS/WO3, MX-CdS, and MX-CdS/WO3; (b) XRD patterns of MX and WO3.

Fig. 2. TEM images of CdS (a), WO3 (b), MX (c), MX-CdS/WO3 (d,f); (e) HRTEM image of MX-CdS/WO3; Elemental mapping (g-m) and EDX spectrum (n) of MX-CdS/WO3.

Fig. 3. XPS scan of Cd 3d (a), S 2p (b), W4f (c), and Ti 2p (d).

Fig. 4. UV-vis absorption spectra (a) and hydrogen evolution (b) of CdS, MX-CdS, CdS/WO3, and MX-CdS/WO3; (c) Recycled photocatalytic H2 evolution experiments of MX-CdS/WO3 and CdS; (d) Apparent quantum efficiency of MX-CdS/WO3.

Fig. 5. (a) PL spectra; (b) EIS Nyquist plots, with inset showing the electrical equivalent circuit of the Nyquist plots; (c) Polarization curves; (d) Photocurrent profiles.

Fig. 6. (a) Fluorescence lifetime spectra of CdS, MX-CdS, CdS/WO3, and MX-CdS/WO3 composites; (b) SPV spectra of CdS, CdS/WO3, and MX- CdS/WO3.

Fig. 7. (a,b) Mott-Schottky plots of CdS and WO3 under dark and light conditions; (c,d) VB XPS profiles of CdS and WO3.

Fig. 8. (a) (αhv)1/2 vs. hν plots of CdS and WO3 from UV-visible DRS analysis; (b) UPS spectra of CdS, WO3, and Ti3C2; (c) Energy level position schematics of CdS and WO3 from the Mott-Schottky plot under dark and light conditions; (d) Band structures of CdS and WO3.

Fig. 9. (a) High-resolution XPS for Cd 3d of CdS/WO3 under 420-nm visible-light irradiation or in the dark; (b) ESR spectra of CdS, WO3, and CdS/WO3 in the dark; (c,d) ESR spectra of CdS, WO3, and CdS/WO3 (DMPO-•O2- and DMPO-•OH-).

Fig. 10. S-scheme heterojunction of MX-CdS/WO3: (a) before contact interaction, (b) after contact interaction, and (c) after contact interaction under irradiation, photogenerated carrier migration and separation, and photocatalytic hydrogen evolution.

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Integration of 2D layered CdS/WO₃ S-scheme heterojunctions and metallic Ti₃C₂ MXene-based Ohmic junctions for effective photocatalytic H₂ generation

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