Citation: Xiao-qiang Cao, Xingyao Liu, Yaqi Wang, Haining Wang, Bo Wei, Yanan Shang, Yizhen Zhang, Yujiao Kan, Yang Zhang, Xing Xu, Longlong Zhang. Surface oxygen vacancy trigger peroxymonosulfate activation with cobalt modified montmorillonite for ofloxacin degradation: The synergistic effect of ¹O₂ and Co(Ⅳ)=O[J]. Chinese Chemical Letters, ;2026, 37(6): 112112. doi: 10.1016/j.cclet.2025.112112 shu

Surface oxygen vacancy trigger peroxymonosulfate activation with cobalt modified montmorillonite for ofloxacin degradation: The synergistic effect of ¹O₂ and Co(Ⅳ)=O

Xiao-qiang Cao ^{a, b} ,
Xingyao Liu ^a ,
Yaqi Wang ^a ,
Haining Wang ^a ,
Bo Wei ^a ,
Yanan Shang ^{a, b} ,
Yizhen Zhang ^{a, b} ,
Yujiao Kan ^{a, b} ,
Yang Zhang ^{a, b} ,
Xing Xu ^c ,
Longlong Zhang ^{a, b, *,}

a.
College of Safety and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
b.
Institute of Yellow River Delta Earth Surface Processes and Ecological Integrity, Shandong University of Science and Technology, Qingdao 266590, China
c.
School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China

llzhang@sdust.edu.cn

Received Date: 15 April 2025
Revised Date: 20 October 2025
Accepted Date: 13 November 2025
Available Online: 14 November 2025

Figures(7)

Oxygen vacancy engineering in heterogeneous catalysts has attracted considerable interest for peroxymonosulfate (PMS) activation. In this study, nano-Co₃O₄-encapsulated montmorillonite catalysts with tunable oxygen vacancy (O_V) concentrations (denoted as Co₃O₄−Mt-xO_V, x = 2, 4, 6) were synthesized for enhanced PMS activation. These O_V defects not only modulate the electronic structure of Co₃O₄ but also strengthen PMS and contaminant adsorption. The optimized Co₃O₄−Mt-xO_V/PMS system exhibited exceptional ofloxacin (OFL) degradation efficiency, achieving 2.74–3.43-fold enhancement over O_V-free Co₃O₄−Mt. Density functional theory calculations and experimental studies revealed that the performance improvement stemmed from O_V formation, which synergistically enhanced redox pair cycling, strengthened PMS adsorption, and promoted active species generation during electron transfer. Further studies demonstrated that O_V sites selectively drive PMS decomposition to generate high-valent cobalt-oxo species (Co(Ⅳ)=O) and singlet oxygen (¹O₂) as the dominant reactive species for OFL oxidation. The in-depth investigation into the catalytic mechanism revealed that the Co(Ⅳ)=O species facilitated O₂^•− generation in surpassing the reaction energy barrier, which subsequently converted to ¹O₂. This non-radical pathway endowed the system with robust anti-interference capability against complex water matrices. The critical role of O_V in PMS activation was mechanistically confirmed through experimental and theoretical analyses. Furthermore, Co₃O₄−Mt-4O_V demonstrated outstanding chemical stability and recyclability, highlighting its practical potential. This work provides fundamental insights into vacancy defect engineering for advanced PMS activation and offers strategic guidance for designing high-performance catalysts.
- Peroxymonosulfate (PMS),
- Co₃O₄,
- Modified montmorillonite,
- Oxygen vacancy,
- Ofloxacin,
- Singlet oxygen (¹O₂),
- High-valent cobalt-oxo species (Co(Ⅳ)=O)
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Surface oxygen vacancy trigger peroxymonosulfate activation with cobalt modified montmorillonite for ofloxacin degradation: The synergistic effect of 1O2 and Co(Ⅳ)=O

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通讯作者: 陈斌, bchen63@163.com

Surface oxygen vacancy trigger peroxymonosulfate activation with cobalt modified montmorillonite for ofloxacin degradation: The synergistic effect of ¹O₂ and Co(Ⅳ)=O