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<p>The rapid recombination of photogenerated charge carriers severely restricts the practical photocatalytic applications of bismuth oxyhalide-based materials. Herein, a facile room-temperature synthesis strategy was developed to successfully fabricate BOBI-X (X = 1, 2, 4, 6, denoting the added volume of glyoxal in mL) solid-solution photocatalysts with oxygen vacancies (OVs) via glyoxal etching. Through comparison, BOBI-4 exhibited the most outstanding photocatalytic performance, achieving a total removal efficiency of 91.68% for 10 mg/L tetracycline (TC) within 90 min (including a 30&#xa0;min dark adsorption phase and a 60-min photocatalytic reaction phase). Notably, the introduction of OVs increases the contribution of superoxide radicals (·O<sub>2</sub><sup>−</sup>) from 29.80% for the pristine sample to 48.43% for the optimized catalyst, making them the primary reactive species confirmed by quenching assays and electron paramagnetic resonance (EPR). Our finding demonstrates that OVs can specifically trigger the massive production of ·O<sub>2</sub><sup>−</sup>, resulting in enhanced enhanced degradation capability towards electron-rich TC molecules. Density functional theory (DFT) calculations further revealed that OVs narrowed the band gap and introduced defect levels within the forbidden band. Finally, combined with theoretical calculations and liquid chromatography-mass spectrometry (LC-MS), the intermediate products, degradation pathways, and toxicity evolution of TC in the photocatalytic system were elucidated. This study provides a theoretical foundation for constructing bismuth oxyhalide-based photocatalysts with efficient ·O<sub>2 </sub><sup>− </sup> production via defect engineering at room-temperature for environmental remediation of antibiotic pollution in aqueous circumstances.</p> Graphical abstract <p></p>

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Oxygen vacancy-mediated BiOBr0.75I0.25 solid solution for efficient removal of emerging contaminants: regulation of charge transfer mechanism and enhanced generation of superoxide radicals

  • 期刊论文

  • 发表日期：

    2026年7月31日

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  • Ziteng Liu,
  • Dong Cui,
  • Qingbang Yang,
  • Mingyue Sun,
  • Dongrun Xie,
  • Bowen Yan,
  • Qi Yang,
  • Zhilin Yang

摘要

The rapid recombination of photogenerated charge carriers severely restricts the practical photocatalytic applications of bismuth oxyhalide-based materials. Herein, a facile room-temperature synthesis strategy was developed to successfully fabricate BOBI-X (X = 1, 2, 4, 6, denoting the added volume of glyoxal in mL) solid-solution photocatalysts with oxygen vacancies (OVs) via glyoxal etching. Through comparison, BOBI-4 exhibited the most outstanding photocatalytic performance, achieving a total removal efficiency of 91.68% for 10 mg/L tetracycline (TC) within 90 min (including a 30 min dark adsorption phase and a 60-min photocatalytic reaction phase). Notably, the introduction of OVs increases the contribution of superoxide radicals (·O2−) from 29.80% for the pristine sample to 48.43% for the optimized catalyst, making them the primary reactive species confirmed by quenching assays and electron paramagnetic resonance (EPR). Our finding demonstrates that OVs can specifically trigger the massive production of ·O2−, resulting in enhanced enhanced degradation capability towards electron-rich TC molecules. Density functional theory (DFT) calculations further revealed that OVs narrowed the band gap and introduced defect levels within the forbidden band. Finally, combined with theoretical calculations and liquid chromatography-mass spectrometry (LC-MS), the intermediate products, degradation pathways, and toxicity evolution of TC in the photocatalytic system were elucidated. This study provides a theoretical foundation for constructing bismuth oxyhalide-based photocatalysts with efficient ·O2 −  production via defect engineering at room-temperature for environmental remediation of antibiotic pollution in aqueous circumstances.

Graphical abstract