Electro-pulsation-generated variable-valent metal triggers alternate pesticide oxidation-chlorinated byproduct reduction on ruthenium-single-atom electrode

Yangqi E; Binyao Wang; Yibo Lin; Huachang Jin; Xueming Chen; Jianmeng Chen; Jin Hur; Yang Yu; Dongzhi Chen

doi:10.1016/j.jhazmat.2025.139052

Electro-pulsation-generated variable-valent metal triggers alternate pesticide oxidation-chlorinated byproduct reduction on ruthenium-single-atom electrode

J Hazard Mater. 2025 Jun 26:495:139052. doi: 10.1016/j.jhazmat.2025.139052. Online ahead of print.

Authors

Yangqi E¹, Binyao Wang¹, Yibo Lin¹, Huachang Jin², Xueming Chen³, Jianmeng Chen⁴, Jin Hur⁵, Yang Yu⁶, Dongzhi Chen⁷

Affiliations

¹ Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, Zhejiang Ocean University, Zhoushan 316022, China; National & Local Joint Engineering Research Center of Harbor Oil & Gas Storage and Transportation Technology, Zhejiang Ocean University, Zhoushan 316022, China.
² National and Local Joint Engineering Research Center, College of Life and Environmental Science, Wenzhou University, Wenzhou 325035, China.
³ College of Environmental and Resources Science, Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, China.
⁴ College of Environmental and Resources Science, Zhejiang University of Science & Technology, Hangzhou 310032, China.
⁵ Department of Environment and Energy, Sejong University, Seoul 05006, South Korea.
⁶ Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, Zhejiang Ocean University, Zhoushan 316022, China; National & Local Joint Engineering Research Center of Harbor Oil & Gas Storage and Transportation Technology, Zhejiang Ocean University, Zhoushan 316022, China. Electronic address: yuyang@zjou.edu.cn.
⁷ Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, Zhejiang Ocean University, Zhoushan 316022, China; National & Local Joint Engineering Research Center of Harbor Oil & Gas Storage and Transportation Technology, Zhejiang Ocean University, Zhoushan 316022, China. Electronic address: chendz@zjou.edu.cn.

PMID: 40578187
DOI: 10.1016/j.jhazmat.2025.139052

Abstract

Anodic oxidation presents a compelling strategy for pesticide-contained wastewater treatment. However, due to the reactive chlorine species-induced side reactions, toxic chlorinated byproducts are prevalent. Herein, a MOF derivative Ru-single-atom electrode, Ru-SbO_X, was specialized for use in electro-pulsation to realize pesticide degradation and in-situ byproduct elimination. The introduction of single-atomic Ru promoted pseudocapacitive Ruⁿ⁺-Sbⁿ⁺ redox conversion, electro-creating metastable high-valent Sb⁵⁺ and low-valent Sb³⁺, then triggering the •OH and •H generation during anodic and cathodic cycles, respectively. This beneficially created an alternating oxidation-reduction environment in an identical electrode, leading to alternate pesticide degradation-byproduct elimination. These allowed Ru-SbO_X to achieve a super-prominent normalized phoxim degradation kinetics constant (3.1 × 10^-6 m·s^-1) in anodic cycles, surpassing other state-of-the-art electrodes; meanwhile, the reactive chlorine species-induced chlorinated byproducts and even N, S, P-related byproducts were in-situ eliminated by at least 10 times in cathodic cycles. This work provides a new perspective for tuning the valence-variable metal in the single-atom electrode to achieve efficient pesticide degradation and in-situ byproduct elimination using the electro-pulsation method.

Keywords: Electro-pulsation; In-situ chlorinated byproduct elimination; Pesticide degradation; Ru-single-atom electrode; Valence-variable metal.