Citation: Enyu Zhao, Xin Tan, Ran Liu, Zihan Yu, Runbin Zeng, Wei Hong, Haiqiang Qi, Xuguang Li, Liangguo Yan, Xing Xu, Wen Song. Heteroatom synergy in N/O dual-doped biochar enhances non-radical degradation in Fenton-like reactions: Mechanisms, practical performance and ecological sustainability[J]. Chinese Chemical Letters, ;2026, 37(5): 111935. doi: 10.1016/j.cclet.2025.111935 shu

Heteroatom synergy in N/O dual-doped biochar enhances non-radical degradation in Fenton-like reactions: Mechanisms, practical performance and ecological sustainability

Enyu Zhao ^a ,
Xin Tan ^b ,
Ran Liu ^a ,
Zihan Yu ^a ,
Runbin Zeng ^a ,
Wei Hong ^b ,
Haiqiang Qi ^a ,
Xuguang Li ^a ,
Liangguo Yan ^a ,
Xing Xu ^c ,
Wen Song ^{a, *,}

a.
School of Water Conservancy and Environment, University of Jinan, Ji'nan 250022, China
b.
Shandong Resources and Environment Construction Group Co. Ltd., Ji'nan 250100, China
c.
Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China

stu_songw@ujn.edu.cn

Received Date: 13 June 2025
Revised Date: 18 August 2025
Accepted Date: 3 October 2025
Available Online: 3 October 2025

Figures(7)

Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBC_BM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBC_BM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (k_obs = 0.1523 min⁻¹) over twice that of NSBC_BM (0.0664 min⁻¹). Radical quenching and electron paramagnetic resonance identified singlet oxygen (¹O₂) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
- Heteroatom doping,
- Peroxymonosulfate,
- Non-radical degradation,
- Toxicity evolution,
- Long-term experiment
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