Citation: Ying Li, Zelin Wu, Xiaoyu Liu, Bingkun Huang, Jing Zhang, Yanbiao Shi, Chuan-Shu He, Zhaokun Xiong, Xingxing An, Bo Lai. Matching molecular scale with active site spacing induces distinct mechanisms in single-atom catalysts for persulfate activation[J]. Chinese Chemical Letters, ;2026, 37(4): 111627. doi: 10.1016/j.cclet.2025.111627 shu

Matching molecular scale with active site spacing induces distinct mechanisms in single-atom catalysts for persulfate activation

Ying Li ^{a, b} ,
Zelin Wu ^{a, b} ,
Xiaoyu Liu ^{a, b} ,
Bingkun Huang ^{a, b} ,
Jing Zhang ^{a, b} ,
Yanbiao Shi ^{a, b} ,
Chuan-Shu He ^{a, b} ,
Zhaokun Xiong ^{a, b, *,} ,
Xingxing An ^{c, *,} ,
Bo Lai ^{a, b}

a.
State Key Laboratory of Hydraulics and Mountain River Engineering, College of Architecture and Environment, Sichuan University, Chengdu 610065, China
b.
Sino-German Centre for Water and Health Research, Sichuan University, Chengdu 610065, China
c.
Department of Endocrinology and Metabolism, West China Hospital, Sichuan University, Chengdu 610041, China

scuxzk@scu.edu.cn

idealangelan@163.com

Received Date: 23 April 2025
Revised Date: 4 June 2025
Accepted Date: 22 July 2025
Available Online: 24 July 2025

Figures(5)

Extensive research has been devoted to single-atom activation of persulfates in recent years. However, mechanistic understanding of the distinct interactions between different persulfates (i.e., peroxymonosulfate (PMS) and peroxydisulfate (PDS)) and the coordination environments of single-atom catalysts (SACs) remains critical for advancing their practical applications. Herein, we developed a Fe-N₄ SAC exhibiting dual activation capabilities for both PMS and PDS. Intriguingly, experimental results revealed divergent activation mechanisms: PMS activation was predominantly mediated via single-site reactions generating singlet oxygen (¹O₂), whereas PDS activation proceeded through both dual-site and single-site pathways involving concurrent ¹O₂ generation and electron transfer processes. Density functional theory calculations further demonstrated that the geometric alignment between the inter-site distances of Fe-N₄ centers and the molecular dimensions of PDS serves as the key determinant for enabling the electron transfer pathway. This fundamental structure-reactivity correlation suggests that the intrinsic molecular-scale differences between PMS and PDS govern their distinct interaction mechanisms with Fe-N₄ SACs. Finally, the scale-up experiments realized nearly complete sulfamethoxazole degradation during 120 h continuous operation without obvious decline in both the Fe-N₄/PMS and Fe-N₄/PDS systems. This work provides fundamental insights into molecular-scale effects on persulfate activation mechanisms, establishing new design principles for SACs optimization in advanced oxidation processes.
- Fenton-like reaction,
- Single-atom catalysts,
- Molecular scale difference effects,
- Dual-site adsorption
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