Bi2O2CO3纳米片晶面工程增强光催化臭氧化: 揭示臭氧吸附与电子转移机制

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

催化学报 ›› 2025, Vol. 72: 143-153.DOI: 10.1016/S1872-2067(24)60270-6

Bi₂O₂CO₃纳米片晶面工程增强光催化臭氧化: 揭示臭氧吸附与电子转移机制

杨洋^a, 杨洲^a, 赖志明^a, 阳灿^a, 侯乙东^a^,^*(), 陶慧琳^b^,^*(), 张金水^a^,^*(), 付贤智^a

^a福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州 350108
^b上饶师范学院化学与环境科学学院, 江西上饶 334001

收稿日期:2024-11-28 接受日期:2025-02-04 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: ydhou@fzu.edu.cn (侯乙东),307183@sur.edu.cn (陶慧琳),jinshui.zhang@fzu.edu.cn (张金水).
基金资助:
国家自然科学基金(22072021);国家自然科学基金(22372036);国家自然科学基金(U21A20326);国家重点研发计划(2018YFA0209301);江西省教育厅科技研究项目(GJJ2201830);111项目(D16008)

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

Yang Yang^a, Zhou Yang^a, Zhiming Lai^a, Can Yang^a, Yidong Hou^a^,^*(), Huilin Tao^b^,^*(), Jinshui Zhang^a^,^*(), Masakazu Anpo^a, Xianzhi Fu^a

^aState Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, Fujian, China
^bSchool of Chemistry and Environmental Science, Shangrao Normal University, Shangrao 334001, Jiangxi, China

Received:2024-11-28 Accepted:2025-02-04 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: ydhou@fzu.edu.cn (Y. Hou), 307183@sur.edu.cn (H. Tao), jinshui.zhang@fzu.edu.cn (J. Zhang).
Supported by:
National Natural Science Foundation of China(22072021);National Natural Science Foundation of China(22372036);National Natural Science Foundation of China(U21A20326);National Key R&D Program of China(2018YFA0209301);Jiangxi Provincial Education Department of Science and Technology Research Project(GJJ2201830);111 Project(D16008)

摘要/Abstract

摘要：

光催化臭氧化技术作为一种新兴的高级氧化工艺, 相较于传统臭氧化技术, 展现出显著提升的氧化效能与环境治理潜力. 光催化臭氧化技术的创新之处在于将光催化与臭氧化进行耦合, 通过光生载流子(e^-与h⁺)驱动臭氧活化, 生成羟基自由基(•OH)和超氧自由基(•O₂^-)等高活性氧物种, 形成多路径氧化网络, 实现污染物的快速降解与深度矿化. 相关研究表明, 该技术可显著降低臭氧投加量并有效控制残留臭氧浓度, 兼具经济性与环境友好性. 然而, 光生电子参与的臭氧还原过程涉及吸附-解离-自由基级联反应等诸多复杂步骤, 其在分子层面的作用机制仍有待进一步明确, 这已然成为制约该技术优化的关键科学难题.

针对光催化臭氧化反应中臭氧活化机制的复杂性, 本文采用晶面工程策略, 深入探究并阐明了催化剂表面结构对臭氧吸附与活化行为所起到的决定性影响. 以层状Bi₂O₂CO₃(BOC)为模型催化剂, 研究发现{110}晶面与{001}晶面凭借差异化的原子排布, 能够调控臭氧吸附特性与反应路径. BOC-{110}吸附臭氧能力强, 可直接解离O₃为表面原子氧(*O)与氧气(O₂), 主导表面直接氧化路径; 而BOC-{001}则具有适中的O₃吸附能力, 有利于光生电子向O₃转移, 形成•O₃^-中间体, 经质子化作用进一步生成•OH与O₂, 主导自由基间接氧化路径. 原位光谱表征证实了这种晶面依赖的臭氧活化差异: 红外光谱监测到吸附在BOC-{001}表面上臭氧(*O₃)在光照条件下被迅速消耗; 拉曼光谱则观察到BOC-{110}表面上*O的累积. 此外, 晶面工程还能调控光催化剂的内建电场, 暴露{001}晶面促进激子的解离以及载流子的分离, 进一步加速了光生电子活化臭氧的动力学过程, 产生更多羟基自由基. 因此, BOC-{001}在光催化臭氧化过程中表现出优异的苯酚矿化率(85%), 明显优于BOC-{110}(53%), 并保持良好的循环稳定性.

综上, 晶面工程在光催化臭氧化体系中的创新性应用, 为高性能催化剂的构筑提供了全新的视角. 通过精准调控催化剂的暴露晶面与表面活性位点, 可实现臭氧吸附强度、光生载流子迁移路径及活性自由基定向生成动力学的多维度优化. 电荷分离效率与臭氧活化效率的同步提升, 成功突破了光催化体系中单电子活化臭氧动力学的速率限制, 进而有望实现难降解有机污染物的深度矿化.

关键词: 光催化臭氧化, 晶面工程, 吸附构型, 臭氧活化, Bi₂O₂CO₃

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

杨洋, 杨洲, 赖志明, 阳灿, 侯乙东, 陶慧琳, 张金水, 付贤智. Bi₂O₂CO₃纳米片晶面工程增强光催化臭氧化: 揭示臭氧吸附与电子转移机制[J]. 催化学报, 2025, 72: 143-153.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60270-6

https://www.cjcatal.com/CN/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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Bi₂O₂CO₃纳米片晶面工程增强光催化臭氧化: 揭示臭氧吸附与电子转移机制

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

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