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

Abstract 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 asy...

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Bibliographic Details
Main Authors: Zhiyong Zhao, Gaohua Yang, Pengfei Wang, Shuai Yue, Mengxue Yang, Tao Zhang, Sihui Zhan
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-60964-2
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Summary:Abstract 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-SO3 -). 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 (CoIV=O), while positively polarized Zn sites drive PMS self-decomposition to generate singlet oxygen (1O2). As a result, the synergistic system of 1O2 and CoIV = 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.
ISSN:2041-1723