Metallic WO2-decorated g-C3N4 nanosheets as noble-metal-free photocatalysts for efficient photocatalysis

doi:10.1016/S1872-2067(22)64210-4

Abstract

Abstract:

The introduction of a metallic cocatalyst is a good strategy for achieving a high carrier density and absorbing photons under wide-spectrum illumination. Herein, metallic WO₂/g-C₃N₄ nanocomposites were designed and synthesized for the first time using a simple calcination method to enhance the photocatalytic performance. WO₂/g-C₃N₄ exhibited significant photocatalytic properties: under visible light irradiation, 4 wt% WO₂/g-C₃N₄ exhibited an RhB photocatalytic degradation of 96% in 120 min. Meanwhile, the H₂ production rate of 4 wt% WO₂/g-C₃N₄/3 wt% Pt was 2436.9 μmol g^-1 h^-1, which was 2.55 and 6.18 times higher than that of 3 wt% Pt/g-C₃N₄ (956.35 μmol g^-1 h^-1) and WO₂/g-C₃N₄, respectively. Experimental tests and density functional theory calculations reveal that WO₂ exhibits a metal-like performance with a narrow bandgap to capture electrons and hinders the recombination of photogenerated charge carriers at the interface of WO₂/g-C₃N₄. Our study provides a new perspective for the rational design of metallic cocatalysts/semiconductors with highly efficient photocatalytic properties.

Key words: g-C₃N₄, Metallic WO₂, Photocatalytic hydrogen production, Photocatalytic degradation, Noble-metal-free photocatalyst

Ning Li, Xueyun Gao, Junhui Su, Yangqin Gao, Lei Ge. Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis[J]. Chinese Journal of Catalysis, 2023, 47: 161-170.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64210-4

https://www.cjcatal.com/EN/Y2023/V47/I4/161

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Fig. 1. (a) XRD patterns of g-C3N4, WO2, and WO2/g-C3N4 nanoparticles. (b) TEM image of 4 wt% WO2/g-C3N4. (c) HRTEM image of 4 wt% WO2/g-C3N4. (d) Mapping image of 4 wt% WO2/g-C3N4/3 wt% Pt.

Fig. 2. XPS spectra of g-C3N4, WO2, and 4 wt% WO2/g-C3N4 nanocomposites. (a) C 1s; (b) N 1s; (c) W 4f; (d) O 1s.

Fig. 3. Photocatalytic properties of the samples under visible irradiation. (a) Photocatalytic degradation activity of RhB. (b) Relationship between ?ln(C/C0) and irradiation time. (c,d) Photocatalytic H2 production performance with 3 wt% Pt as cocatalyst. (e) Cycle experiments of 4 wt% WO2/g-C3N4 for the photodegradation of RhB. (f) Cycle experiment data of the photocatalytic H2 production activity of the 4 wt% WO2/g-C3N4/3 wt% Pt photocatalyst.

Fig. 4. Transient photocurrent response curves (a), EIS spectra (b), PL spectra (c), and TRPL spectra (d) of g-C3N4, WO2, and 4 wt% WO2/g-C3N4 samples.

Fig. 5. (a) UV-vis diffuse reflectance spectra. (b) DRS band gap and UV-Vis-near-infrared absorption spectra (inset image). (c) Mott-Schottky plots of g-C3N4, WO2, and 4 wt% WO2/g-C3N4. (d) Band structures of g-C3N4 and WO2.

Fig. 6. Energy band structure (a) and DOS mapping (b) of g-C3N4; energy band structure (c) and DOS mapping (d) of WO2.

Fig. 7. ESR spectra of the 4 wt% WO2/g-C3N4 photocatalyst at room temperature. (a) e?; (b) H+; (c) ?O2-; (d) ?OH.

Fig. 8. Electrostatic potentials of g-C3N4 (a) and WO2 (111) surfaces (b).

Scheme 1. Possible photocatalytic mechanism under visible light illumination. (a) Photodegradation mechanism; the middle part represents the work functions of g-C3N4 and WO2 before contact. (b) Photocatalytic H2 production process.

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Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis

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