Construction of ultrathin BiVO4 nanosheets with bismuth-oxygen dual vacancies for photocatalytic nitrogen reduction

doi:10.1016/S1872-2067(25)64808-X

Abstract

Abstract:

The efficient utilization of photogenerated electrons and the effective activation of reactive molecules are among the major challenges in photocatalytic nitrogen reduction. Defect engineering can enhance the catalyst's ability to adsorb and activate N₂ and H₂O, while the ultrathin structure with maximized active crystal facets can maximize the enrichment of effective photogenerated electrons. This work employs a two-step synergistic method to fabricate ultrathin BiVO₄ with oxygen vacancies and bismuth vacancies (2D-V_Bi+O-BVO, thickness < 20 nm) for photocatalytic nitrogen reduction. Scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy characterization confirm the transformation of BiVO₄ from bulk material (bulk-BVO, ~1300 nm) to an ultrathin structure (~15 nm). TEM, X-ray photoelectron spectroscopy, electron paramagnetic resonance characterizations, and density functional theory (DFT) calculations verify the construction of oxygen and bismuth vacancies in the ultrathin BiVO₄. Compared to bulk-BVO, the photocatalytic nitrogen fixation efficiency of 2D-V_Bi+O-BVO is increased by 4.7 times, with the highest activity reaching 158.73 μmol·g^-1·h^-1. N₂-temperature programmed desorption and DFT calculations demonstrate that the oxygen and bismuth vacancies in BiVO₄, respectively, promote the adsorption/activation of N₂ and H₂O, which is crucial for the overall nitrogen reduction reaction. Photo-deposition experiments prove that the (040) plane is the active surface for electrons. And the ultrathin structure maximizes the (040) facet of BiVO₄, which is conducive to the high enrichment of electrons. Meanwhile, more active sites can be exposed for the activation of N₂ and H₂O. In situ infrared spectroscopy confirms that N₂ can be effectively adsorbed onto 2D-V_Bi+O-BVO, and the presence of NH₂-NH₂ active species is consistent with the alternating reaction pathway. This study provides new insights into the development of green and efficient photocatalysts with dual vacancies and ultrathin structures.

Key words: Oxygen vacancies, Bismuth vacancies, Ultrathin structures, Photocatalysis, Nitrogen reduction

Jiahui Chen, Yue Meng, Bo Xie, Zheming Ni, Shengjie Xia. Construction of ultrathin BiVO₄ nanosheets with bismuth-oxygen dual vacancies for photocatalytic nitrogen reduction[J]. Chinese Journal of Catalysis, 2025, 78: 265-278.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64808-X

https://www.cjcatal.com/EN/Y2025/V78/I11/265

Figures/Tables 8

Fig. 1. (a-d) SEM images of different samples. TEM image (e), EDS image (f), and HRTEM (g,h) images of 2D-VBi+O-BVO. (i) XRD patterns of different samples.

Fig. 2. (a-c) SEM images of different samples. (d) Schematic illustration of the ultrathin structure of BiVO4. TEM image (e), AFM image (f), height distribution image (g), and high sensor image (h) of 2D-VBi+O-BVO.

Fig. 3. HRTEM image (a), Fourier inverse transform image (b), atomic gradient image (c), and DFT models image (d) of 2D-VBi+O-BVO. (e) XPS spectra of different samples. High-resolution XPS spectra for V (f), Bi 4f (g) and O 1s (h) of different samples. (i) EPR spectra of different samples.

Table 1 Relative elemental content analysis of bulk-BVO, 2D-VO-BVO, VBi-BVO, and 2D-VBi+O-BVO.

Sample	Bi atom%	O atom %	V atom %	Bi:O:V
bulk-BVO	17.61%	71.51%	10.88%	1.6:6.6:1
2D-V_O-BVO	19.59%	69.61%	10.80%	1.8:6.4:1
V_Bi-BVO	6.64%	73.79%	19.57%	0.3:3.7:1
2D-V_Bi+O-BVO	13.85%	71.07%	15.08%	0.9:4.7:1

Fig. 4. (a) Photocatalytic nitrogen fixation activity of different samples. (b) By-products content in photocatalytic nitrogen fixation of 2D-VBi+O-BVO. (c) The NH3 yield of 2D-VBi+O-BVO under different conditions. (d) The results of 15N2 isotope labeling by NMR spectrum. (e) Photocatalytic ammonia production rates for cyclic tests of 2D-VBi+O-BVO. (f) The NH3 yield of 2D-VBi+O-BVO over time. DRS spectra and tauc plots of (αhv)1/2 versus energy (hν) (g), valence-band spectra (h), schematic diagrams (i) of the band structure for different samples.

Fig. 5. Photocurrent response curves (a) and EIS (b) of different samples. (c) PL spectra of bulk-BVO and 2D-VBi+O-BVO. (d,e) SEM image and element mapping of photo-deposited Ag on bulk-BiVO4. (f) Schematic illustration of the ultrathin structural transformation. N2 adsorption-desorption isotherm (g) and N2-TPD spectra (h) of bulk-BVO and 2D-VBi+O-BVO. (i) In-situ FTIR spectra of the N2 photoreduction reaction with 2D-VBi+O-BVO.

Fig. 6. (a-c) The in-situ FTIR spectra of the samples in different ranges as a function of time. (d,e) the distal and alternative binding pathways for the N2 reduction on 2D-VBi+O-BVO. The DFT adsorption models of N2 molecules (f,g) and H2O molecules (h,i) on bulk-BVO and 2D-VBi+O-BVO. Purple, grey, red, blue, and yellow spheres denote Bi, V, O, N, and H atoms, respectively.

Fig. 7. The photocatalytic ammonia synthesis mechanism of ultrathin BiVO4 with bismuth and oxygen dual vacancies.

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Construction of ultrathin BiVO₄ nanosheets with bismuth-oxygen dual vacancies for photocatalytic nitrogen reduction

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