Regulating nonradicals generation through peroxymonosulfate activation via localized dipole to enhance wastewater biodegradability

• Published in: Nature communications Vol. 16; no. 1; pp. 5861 - 12
• Main Authors: Zhao, Zhiyong, Yang, Gaohua, Wang, Pengfei, Yue, Shuai, Yang, Mengxue, Zhang, Tao, Zhan, Sihui
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.07.2025; Nature Publishing Group; Nature Portfolio
• Subjects: 140/133; 140/146; 147/135; 147/143; 639/638/169/896; 639/638/77/887; Aniline; Aniline Compounds - chemistry; Asymmetric structures; Biochemical oxygen demand; Biodegradability; Biodegradation; Biodegradation, Environmental; Catalysis; Catalysts; Charge density; Chemical oxygen demand; Cobalt; Cobalt - chemistry; Contaminants; Dipoles; Electron distribution; Electron transfer; Electrons; Humanities and Social Sciences; Hydrogen bonds; multidisciplinary; Oxidation; Oxygen; Peroxides - chemistry; Pollutants; Reactors; Science; Science (multidisciplinary); Singlet oxygen; Singlet Oxygen - chemistry; Spectrum analysis; Sulfur trioxide; Symmetry; Transmission electron microscopy; Wastewater; Wastewater - chemistry; Water Pollutants, Chemical - chemistry; Water pollution; Water Purification - methods; Zinc oxide; Zinc Oxide - chemistry
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-025-60964-2

It is still greatly desirable to activate peroxymonosulfate (PMS) forming nonradicals for the removal of electron-rich contaminants in complex water matrices. However, achieving this on heterogeneous metal-based catalysts with uniform electron distribution remains challenging due to the asymmetric structure of PMS molecules (H-O-O-SO 3 - ). Here, inspired by the dipole effect, we design a Co-doped ZnO catalyst (ZOC) to break charge symmetry at active sites and enhance nonradicals generation. The high charge density at Co sites facilitates two-electron transfer, promoting O-O and O-H bond cleavage to form high-valent cobalt-oxo (Co IV =O), while positively polarized Zn sites drive PMS self-decomposition to generate singlet oxygen ( 1 O 2 ). As a result, the synergistic system of 1 O 2 and Co IV  = O results in a k-value of 73.93 min⁻¹ M⁻¹ for aniline (AN) degradation, 189.6 times higher than ZnO/PMS (ZO/PMS), and also shows a high selectivity for electron-rich new pollutants. The practicality of this outstanding nonradicals system is confirmed by a significant increase in biochemical oxygen demand/chemical oxygen demand (BOD/COD) of the mixed wastewater to over 0.55 in the air-lifting internal circulating reactor. This study offers a structural regulation for controlling catalytic functionality and provides general guidelines for designing Fenton-like reactors to enhance wastewater biodegradability. A Co-doped ZnO catalyst is developed to break charge symmetry at active sites, promoting the activation of peroxymonosulfate to generate nonradical species for efficient removal of electron-rich pollutants in complex water environments.