Citation: Fuming Miao, Zexiang Gao, Ting Cheng, Cibin Wang, Youzhi Liu, Xingyue Wei, Xinping Duan, Weizhou Jiao. Sulfur-nitrogen synergy anchored and modulated cobalt nanoparticles to construct dual micro-reduction environments for efficient peroxymonosulfate activation: Nonradical-dominated mechanism[J]. Chinese Chemical Letters, ;2026, 37(7): 112676. doi: 10.1016/j.cclet.2026.112676 shu

Sulfur-nitrogen synergy anchored and modulated cobalt nanoparticles to construct dual micro-reduction environments for efficient peroxymonosulfate activation: Nonradical-dominated mechanism

Fuming Miao ^a ,
Zexiang Gao ^a ,
Ting Cheng ^a ,
Cibin Wang ^a ,
Youzhi Liu ^a ,
Xingyue Wei ^a ,
Xinping Duan ^b ,
Weizhou Jiao ^{a, *,}

a.
Shanxi Province Key Laboratory of Chemical Process Intensification, State Key Laboratory of Coal and CBM Co-Mining, School of Chemistry and Chemical Engineering, North University of China, Taiyuan 030051, China
b.
Department of Chemistry, College of Chemistry and Chemical Engineering, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, Xiamen University, Xiamen 361005, China

zbdxjwz@nuc.edu.cn

Received Date: 9 October 2025
Revised Date: 22 January 2026
Accepted Date: 24 March 2026
Available Online: 24 March 2026

Figures(6)

To address the challenges of active metal leaching and sluggish redox cycling in heterogeneous metal-catalyzed peroxymonosulfate (PMS) activation, this study proposes a double heteroatom co-anchoring and regulation strategy to design a sulfur-nitrogen co-doped carbon-supported cobalt nanoparticle catalyst (Co-S-CN). This strategy successfully constructs a “S^2--Co⁰” dual micro-reduction environment, significantly accelerating the Co³⁺/Co²⁺ redox cycle. Experimental results demonstrate that the Co-S-CN+PMS system achieves 100% phenol degradation within 5 min while exhibiting exceptional resistance to anion interference (SO₄²⁻, Cl⁻, HCO₃⁻, H₂PO₄⁻). Low cobalt leaching rate (<1%) across various pH conditions confirms strong metal anchoring via S-N synergy. Structural characterizations verify the existence of S^2- and Co⁰, and co-optimizing cobalt valence cycling. Electron paramagnetic resonance (EPR) and quenching experiments indicate the reaction proceeds primarily via a nonradical pathway, with singlet oxygen (¹O₂) as the key reactive species. Density functional theory (DFT) calculations reveal that S-N synergy enhances PMS adsorption strength (adsorption energy optimized from −3.51 eV to −3.77 eV), increases charge density (Bader charge increased from 0.75 e to 0.80 e), and optimizes the electronic structure of Co 3d orbitals (d-band center upshifted from −1.341 eV to −1.330 eV). This work provides a strategy for rational design of highly active and stable catalysts.
- Cobalt nanoparticles,
- Peroxymonosulfate,
- Nonradical,
- Sulfur-nitrogen co-anchoring,
- Redox cycle
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