Plasma-exfoliated g-C<sub>3</sub>N<sub>4</sub> with oxygen doping: tailoring photocatalytic properties

doi:10.1007/s11705-023-2381-1

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (2) : 15 https://doi.org/10.1007/s11705-023-2381-1

Plasma-exfoliated g-C₃N₄ with oxygen doping: tailoring photocatalytic properties

Yuxin Li, Junxin Guo, Rui Han, Zhao Wang(

)

National Engineering Research Centre of Industry Crystallization Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

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Abstract

Heteroatom doping and defect engineering have been proposed as effective ways to modulate the energy band structure and improve the photocatalytic activity of g-C₃N₄. In this work, ultrathin defective g-C₃N₄ was successfully prepared using cold plasma. Plasma exfoliation reduces the thickness of g-C₃N₄ from 10 nm to 3 nm, while simultaneously introducing a large number of nitrogen defects and oxygen atoms into g-C₃N₄. The amount of doped O was regulated by varying the time and power of the plasma treatment. Due to N vacancies, O atoms formed strong bonds with C atoms, resulting in O doping in g-C₃N₄. The mechanism of plasma treatment involves oxygen etching and gas expansion. Photocatalytic experiments demonstrated that appropriate amount of O doping improved the photocatalytic degradation of rhodamine B compared with pure g-C₃N₄. The introduction of O optimized the energy band structure and photoelectric properties of g-C₃N₄. Active species trapping experiments revealed ·O₂^– as the main active species during the degradation.

Keywords graphitic carbon nitride cold plasma oxygen doping nitrogen defect visible-light photocatalysis

Corresponding Author(s): Zhao Wang

Just Accepted Date: 06 November 2023 Issue Date: 03 January 2024

Cite this article:

Yuxin Li,Junxin Guo,Rui Han, et al. Plasma-exfoliated g-C₃N₄ with oxygen doping: tailoring photocatalytic properties[J]. Front. Chem. Sci. Eng., 2024, 18(2): 15.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2381-1
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I2/15

Fig.1 XRD and FTIR characterization of samples: (a) XRD patterns; (b) FTIR spectra.

Fig.2 SEM and TEM images of (a, c) CN, (b, d) OCN-100-6; AFM images and corresponding height curves of (e, g) CN, (f, h) OCN-100-6.

Fig.3 The specific surface area and pore structure of catalysts: (a) N₂ adsorption-desorption isotherms, (b) pore analysis.

Tab.1 Percentage values of peak area in high-resolution XPS spectrum

Fig.4 High-resolution XPS spectra for C 1s, N 1s and O 1s: (a, c, e) with different plasma treatment time; (b, d, f) with different plasma power.

Tab.2 Percentage of oxygen for CN and OCN samples

Fig.5 EPR and mass spectrometry of the samples: (a) EPR spectra of CN, OCN-100-6 and DCN-100-6; (b) online mass spectrogram of OCN-100-6 during plasma treatment.

Fig.6 Diagram of formation mechanism of nitrogen defects and oxygen doping in carbon nitride during the plasma treatment.

Fig.7 The photocatalytic activity of the catalysts: (a), (b) photocatalytic degradation of RhB over the catalysts; (c) kinetics of RhB degradation by plotting ln(C₀/C_t) vs. irradiation times; (d) the photodegradation stability of RhB over OCN-100-6.

Fig.8 The photoelectric properties of the catalysts: (a) UV-Vis DRS, (b) the band gap energies, (c) M–S plots, (d) PL spectra, (e) EIS and (f) transient photocurrent responses of CN and OCN-100-6.

Fig.9 The active species testing: (a) radicals capture experiments for photocatalytic degradation of RhB over OCN-100-6; BQ, benzoquinone; IPA, isopropanol; (b) DMPO-·O₂^? and (c) DMPO-·OH of ESR spectra over OCN-100-6 in dark and light conditions.

Fig.10 Proposed mechanism for photocatalytic degradation of RhB over OCN-100-6.

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