Electron-transfer pathways insights into contaminants oxidized by Cu-OOSO3- intermediate: Effects of oxidation states of Cu and solution pH values

Lele Zhao; Jiaming Zhang; Zhiping Zhang; Yujun Zhu; Yuan Zong; Chengying Bai; Tong Wei; Yueming Ren; Jun Ma

doi:10.1016/j.jhazmat.2023.130881

Electron-transfer pathways insights into contaminants oxidized by Cu-OOSO₃^- intermediate: Effects of oxidation states of Cu and solution pH values

J Hazard Mater. 2023 Apr 15:448:130881. doi: 10.1016/j.jhazmat.2023.130881. Epub 2023 Jan 27.

Authors

Lele Zhao¹, Jiaming Zhang¹, Zhiping Zhang², Yujun Zhu³, Yuan Zong¹, Chengying Bai¹, Tong Wei¹, Yueming Ren⁴, Jun Ma⁵

Affiliations

¹ Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China.
² School of Materials Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China.
³ Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials, Heilongjiang University, Harbin 150080, China.
⁴ Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China. Electronic address: renyueming@hrbeu.edu.cn.
⁵ State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China. Electronic address: majun@hit.edu.cn.

PMID: 36758434
DOI: 10.1016/j.jhazmat.2023.130881

Abstract

The copper-peroxy complex (Cu-OOSO₃^-) metastable intermediate has been confirmed to oxidize contaminants via a single-electron-transfer pathway or an oxygen-atom-transfer pathway. And the effects of Cu oxidation states and reaction pH conditions on the intermediate properties have not been explored in depth. Here, copper oxide (CuO_x) catalysts with different Cu oxidation states were synthesized by a simple precipitation method by controlling the reaction temperature from 0 to 45 °C. CuO_x displayed a strong catalytic dependence on the Cu oxidation state, and CuO_x-30 with Cu average valence on the catalyst surface of 1.61 was more reactive for catalytic degradation of bisphenol A with peroxymonosulfate (PMS). Notably, CuO_x-30, with the best electron-accepting ability, was easier to bonding with PMS to form the Cu-OOSO₃^- reactive complex, and the generated intermediate exhibited the strongest capacity to obtain electrons from contaminants. Moreover, the electron-transfer pathways were closely related to the average valence of Cu, and the contribution of the oxygen-atom-transfer pathway changed volcanic with increasing Cu valence. Meanwhile, the reaction predominantly involved the oxygen-atom-transfer pathway under acidic conditions (pH=3), while the contribution of the single-electron-transfer pathway raised with increasing pH values. Hence, this work was devoted to providing new insights into the CuO_x-inducing PMS activation and vital supplementary to the properties of the Cu-OOSO₃^- intermediate.

Keywords: 6Cu-OOSO(3)(-) intermediate; CuO(x) catalysts; Oxygen-atom-transfer; Peroxymonosulfate; Single-electron-transfer.