Enhanced photocatalytic performance by regulating the Ce<sup>3+</sup>/Ce<sup>4+</sup> ratio in cerium dioxide

doi:10.1007/s11705-024-2394-4

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (3) : 31 https://doi.org/10.1007/s11705-024-2394-4

Enhanced photocatalytic performance by regulating the Ce³⁺/Ce⁴⁺ ratio in cerium dioxide

Zhi Li, Dongsheng Jia, Wei Zhang, Ying Li, Mitang Wang, Dongliang Zhang(

)

School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China

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Abstract

Cerium dioxide (CeO₂) photocatalysts are used in treating environmental pollution and addressing the energy crisis due to their excellent oxygen storage capacities and abundant oxygen vacancies. In this paper, CeO₂ precursors were synthesized with different water-alcohol ratios via a solvothermal method, and CeO₂ photocatalysts with different Ce³⁺/Ce⁴⁺ ratios were obtained by changing the precursor calcination atmospheres (air, Ar) as well as the calcination time. The effects of CeO₂ with different Ce³⁺/Ce⁴⁺ ratios in photocatalytic degradations of methylene blue under visible light were investigated. X-ray photoelectron spectroscopy results showed that the surfaces of the samples calcined under Ar had higher Ce³⁺/Ce⁴⁺ ratios and oxygen vacancy concentrations, which reduced the band gaps of the catalysts and improved their utilization of visible light. In addition, the many Ce³⁺/Ce⁴⁺ redox centers and oxygen vacancies on the sample surfaces improved the separation and transfer efficiencies of the photogenerated carriers. The sample C2-Ar calcined under Ar showed a high adsorption capacity and excellent photocatalytic activity by removing 96% of the methylene blue within 120 min, which was more than twice the degradation rate of the sample (C2-air) prepared via calcination under air. Trapping experiments showed that photogenerated holes played a key role in the photocatalytic process. In addition, a synergistic photocatalytic mechanism for the Ce³⁺/Ce⁴⁺ redox centers and oxygen vacancies was elucidated in detail, and the sensitization of cerium dioxide by dyes aided the degradation of methylene blue.

Keywords CeO₂ oxygen vacancies Ce³⁺/Ce⁴⁺ ratios photocatalytic dye-sensitization

Corresponding Author(s): Dongliang Zhang

Just Accepted Date: 21 December 2023 Issue Date: 06 February 2024

Cite this article:

Zhi Li,Dongsheng Jia,Wei Zhang, et al. Enhanced photocatalytic performance by regulating the Ce³⁺/Ce⁴⁺ ratio in cerium dioxide[J]. Front. Chem. Sci. Eng., 2024, 18(3): 31.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2394-4
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I3/31

Fig.1 XRD patterns of different CeO₂ samples.

Tab.1 Calculation of structural parameters for different CeO₂ samples

Fig.2 SEM images of (a) C1-air, (b) C2-air, (c) C2-air-3, (d) C3-air, (e) C1-Ar, (f) C2-Ar and (g) C3-Ar.

Fig.3 C2-air and C2-Ar of (a) N₂ adsorption-desorption isotherms and (b) Barrett-Joyner-Halenda (BJH) pore size distribution curves.

Fig.4 XPS spectra of (a) Ce 3d precursors C-10:30, C-10:60 and C-10:90, XPS spectra of CeO₂ under air atmosphere calcination of (b) Ce 3d and (c) O 1s, XPS spectra of CeO₂ under Ar atmosphere calcination of (d) Ce 3d and (e) O 1s, and (f) Ce³⁺ and oxygen vacancies of different CeO₂ samples content.

Fig.5 Different CeO₂ samples of (a) Raman spectra and (b) PL spectra.

Fig.6 Different CeO₂ samples of (a) UV-Vis DRS and (b) Tauc plots.

Fig.7 (a) TPC response and (b) electrochemical impedance of different Ce dioxide.

Fig.8 (a) Effect of different CeO₂ samples on MB degradation rate, (b) the pseudo-first-order reaction kinetics for MB degradation, (c) cycling test for MB degradation on C2-Ar samples and (d) effect of different scavengers on the degradation MB of C2-Ar samples.

Tab.2 Comparison of photocatalysts with previously reported materials for MB degradation rate (%)

Fig.9 Degradation of MB by (a) C2-air and (b) C2-Ar at different wavelengths of light.

Fig.10 Schematic diagram of the possible photocatalytic mechanism of cerium dioxide with oxygen-rich vacancies.

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