Diatomic "catalytic/co-catalytic" Fe/Mo catalysts promote Fenton-like reaction to treat organic wastewater through special interfacial reaction enhancement mechanism

Zhen Liu; Xin-Yi Xu; Fei Xu; Rui-Dian Su; Bin Li; Fang Zhang; Xing Xu; Yan Wang; De-Fang Ma; Bao-Yu Gao; Qian Li

doi:10.1016/j.watres.2025.123147

Diatomic "catalytic/co-catalytic" Fe/Mo catalysts promote Fenton-like reaction to treat organic wastewater through special interfacial reaction enhancement mechanism

Water Res. 2025 Jan 14:274:123147. doi: 10.1016/j.watres.2025.123147. Online ahead of print.

Authors

Zhen Liu¹, Xin-Yi Xu¹, Fei Xu², Rui-Dian Su³, Bin Li⁴, Fang Zhang⁵, Xing Xu¹, Yan Wang¹, De-Fang Ma¹, Bao-Yu Gao¹, Qian Li⁶

Affiliations

¹ Shandong Key Laboratory of Water Pollution Control and Resource Reuse, Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao 266200, China.
² Environmental Research Institute, Shandong University, Qingdao 266200, China.
³ Shandong Key Laboratory of Water Pollution Control and Resource Reuse, Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao 266200, China; College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China.
⁴ CAS Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China.
⁵ National Engineering Research Center for Nanotechnology, Shanghai 200241, China.
⁶ Shandong Key Laboratory of Water Pollution Control and Resource Reuse, Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao 266200, China. Electronic address: qianli@sdu.edu.cn.

PMID: 39826398
DOI: 10.1016/j.watres.2025.123147

Abstract

The full utilization of active sites and the effective Fe²⁺/Fe³⁺cycling are the key problems that expand the application of iron-based Fenton-like reaction in water purification. In this paper, a novel diatomic Fe/Mo catalyst (Fe/Mo-DACs) was used to enhance the interfacial reaction mechanism with oxidant to achieve more stronger selective degradation of electron-donating organic pollutants. The availability of Fe sites during the activation of peroxymonosulfate (PMS) was enhanced by the adjacent atomic Mo sites, and the resulting special interfacial complex (Fe/Mo-DACs-PMS*) possessed higher activity, stability and selectivity (especially for electron-donating organics). The degradation rate of bisphenol A (BPA) in Fe/Mo-DACs/PMS system (0.642 min^-1) was increased by two times compared with the corresponding Fe single-atomic reaction system. Density functional theory calculation analysis further indicated that the diatomic Fe/Mo site was the true activation center of PMS, and other independent single-atom Fe sites cooperated to optimize the interface reaction mechanism (adsorption and activation) of PMS on the materials' surface. Moreover, the promotion of Fe²⁺/Fe³⁺ cycling by Mo sites further enhanced the sustainability and adaptability of this degradation system. The atomic-level "catalytic/co-catalytic" materials are expected to broaden the design idea of heterogeneous materials and enhance the application prospect of Fenton-like reactions in water pollution control.

Keywords: Diatomic Fe/Mo sites; Electron transfer process; Fe(2+)/Fe(3+) cycle; Fenton-like reaction; Selective degradation.