Cu-doped Bi/Bi2WO6 catalysts for efficient N2 fixation by photocatalysis

doi:10.1007/s11705-023-2312-1

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (10) : 1412-1422 https://doi.org/10.1007/s11705-023-2312-1

RESEARCH ARTICLE

Cu-doped Bi/Bi₂WO₆ catalysts for efficient N₂ fixation by photocatalysis

Xiaojing Li¹, Chunran Zhao¹, Junfeng Wang¹, Jiayu Zhang³, Ying Wu³(

), Yiming He^1,²(

)

¹. Department of Materials Science and Engineering, Zhejiang Normal University, Jinhua 321004, China
². Key Laboratory of Solid State Optoelectronic Devices of Zhejiang province, Zhejiang Normal University, Jinhua 321004, China
³. Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China

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Abstract

In this paper, Cu-doped Bi₂WO₆ was synthesized via a solvothermal method and applied it in photocatalytic N₂ immobilization. Characterization results showed the presence of a small amount of metallic Bi in the photocatalyst, indicating that the synthesized photocatalyst is actually Bi/Cu-Bi₂WO₆ composite. The doped Cu had a valence state of +2 and most likely substituted the position of Bi³⁺. The introduced Cu did not affect the metallic Bi content, but mainly influenced the energy band structure of Bi₂WO₆. The band gap was slightly narrowed, the conduction band was elevated, and the work function was reduced. The reduced work function improved the transfer and separation of charge carriers, which mainly caused the increased photoactivity. The optimized NH₃ generation rates of Bi/Cu-Bi₂WO₆ reached 624 and 243 μmol·L^–1·g^–1·h^–1 under simulated solar and visible light, and these values were approximately 2.8 and 5.9 times higher those of Bi/Bi₂WO₆, respectively. This research provides a method for improving the photocatalytic N₂ fixation and may provide more information on the design and preparation of heteroatom-doped semiconductor photocatalysts for N₂-to-NH₃ conversion.

Keywords Bi₂WO₆ Cu doping work function photocatalytic N₂ fixation charge separation

Corresponding Author(s): Ying Wu,Yiming He

Just Accepted Date: 10 May 2023 Online First Date: 28 June 2023 Issue Date: 07 October 2023

Cite this article:

Xiaojing Li,Chunran Zhao,Junfeng Wang, et al. Cu-doped Bi/Bi₂WO₆ catalysts for efficient N₂ fixation by photocatalysis[J]. Front. Chem. Sci. Eng., 2023, 17(10): 1412-1422.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2312-1
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I10/1412

Fig.1 (a) XRD patterns and (b) Raman spectra of BWO-S and Cu-BWO composites.

Fig.2 SEM images of (a) BWO-S, (b) SEM, (c) EDS mapping, and (d, e) TEM pictures of (f) 2% Cu-BWO composite.

Fig.3 XPS spectra of BWO-S and 2% Cu-BWO composite. (a) Cu 2p; (b) Bi 4f; (c) W 4f; (d) O 1s.

Fig.4 (a) DRS spectra and (b) the estimated band gaps of BWO-S and Cu-BWO.

Fig.5 (a) MS plots, (b) transient PC response and (c) EIS profiles of BWO-S and Cu-BWO photocatalysts.

Fig.6 Photocatalytic activity of BWO-S and Cu-BWO composites under (a) simulated solar light and (b) visible light, (c) the cyclic test of 2% Cu-BWO and (d) ¹H NMR spectra (600 MHz) of the reaction solution in the presence of BWO and 2% Cu-BWO.

Fig.7 Band diagrams of Bi₂WO₆ and Cu-doped Bi₂WO₆ photocatalysts.

Fig.8 LSV profiles of BWO-S and 2% Cu-BWO under Ar and N₂ atmosphere.

Fig.9 Possible mechanism of Cu-BWO composites in photocatalytic N₂ fixation.

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