Crystal facet engineering of Bi2O2CO3 nanosheets to enhance photocatalytic ozonation: Unraveling ozone adsorption and electron transfer mechanism

doi:10.1016/S1872-2067(24)60270-6

Abstract

Abstract:

Photocatalytic ozonation holds promise for advanced water purification, yet its development has been hindered by a limited understanding of ozone activation mechanisms and its related photogenerated electron transfer dynamics. Herein, we employed in-situ DRIFTS and Raman spectroscopy to elucidate the distinct adsorption and activation behaviors of ozone (O₃) on the {001} and {110} crystal facets of Bi₂O₂CO₃ (BOC) nanosheets. BOC-{001} demonstrates superior photocatalytic ozonation performance, with 85% phenol mineralization and excellent durability, significantly outperforming the 53% mineralization rate of BOC-{110}. This enhanced activity is attributed to non-dissociative ozone adsorption and favorable adsorption energy over {001} facet, which facilitate the one-electron O₃ reduction pathway. Furthermore, crystal facet engineering strengthens the built-in electric field, promoting exciton dissociation and the generation of localized charge carriers. The synergistic effects of optimized electron availability and ozone adsorption significantly boost the production of reactive oxygen species. These findings provide a deeper understanding of the critical roles of O₃ adsorption and electron transfer in radical generation, which could provide some guidance for the strategic development of highly effective photocatalytic ozonation catalysts.

Key words: Photocatalytic ozonation, Crystal facets, Adsorption configuration, O₃ activation, Bi₂O₂CO₃

Yang Yang, Zhou Yang, Zhiming Lai, Can Yang, Yidong Hou, Huilin Tao, Jinshui Zhang, Masakazu Anpo, Xianzhi Fu. Crystal facet engineering of Bi₂O₂CO₃ nanosheets to enhance photocatalytic ozonation: Unraveling ozone adsorption and electron transfer mechanism[J]. Chinese Journal of Catalysis, 2025, 72: 143-153.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60270-6

https://www.cjcatal.com/EN/Y2025/V72/I5/143

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Fig. 1. (a) XRD patterns of the BOC catalysts. (b) High-resolution XPS spectra for O 1s. (c) SEM image of BOC-{110). (d) SEM image of BOC-{001). (e) HR-TEM image of BOC-{110). (f) HR-TEM image of BOC-{001).

Fig. 2. (a) Phenol degradation rates in different oxidation processes using BOC catalysts. (b) Pseudo-first-order reaction constants of BOC catalysts. (c) TOC removal rate in different oxidation processes on BOC catalysts. (d) Final TOC removal rates in within 80 min. (e) Activity stability of BOC-{001} catalyst. (f) Photocatalytic ozonation performance of BOC-{001} catalyst for different target phenolic pollutants removal.

Fig. 3. Electron difference density map of {110} facet (a) and {001} facet (b). (c) Surface potential of the BOC catalysts. (d) Zeta potential and BIEF intensity of the BOC catalysts. Integrated PL emission intensity as a function of temperature from 10 to 300 K of BOC-{110} (e) and BOC-{001} (f). (g) Phosphorescence spectra of the BOC catalysts. (h) Schematic diagram of BIEF-promoted exciton dissociation.

Fig. 4. Trapping EPR spectra of ?OH (a), ?O2- (b), and 1O2 (c). (d) Comparative analysis of pseudo-first-order reaction constants for phenol degradation in the presence of various radical scavengers. (e) Variations in the OA content among the phenol degradation intermediates across diverse oxidation processes. (f) Impact of various free radical scavengers on the oxalic acid degradation efficiency.

Fig. 5. O3 adsorption configuration on the {110} facet (a) and {001} facet (b). (c,d) In situ DRIFTS spectra of the BOC catalysts under varying atmospheres. (e) In situ Raman spectra of the BOC catalysts. (f) Schematic diagram of O3 activation mechanism on the {110} and {001} facets.

Fig. 6. Charge difference iso-surfaces of the O3 molecule on BOC-{110} (a) and BOC-{001} (b). The electron transfer number of the BOC-{110} (c) and BOC-{001} (d).(e,f) Open-circuit potential tests of the BOC catalysts. (g) Reaction mechanism illustration of the photocatalytic ozonation reaction on the BOC catalysts.

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Crystal facet engineering of Bi₂O₂CO₃ nanosheets to enhance photocatalytic ozonation: Unraveling ozone adsorption and electron transfer mechanism

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