Peroxymonosulfate activation for the efficient removal of organic pollutant by ZIF-67-derived low-crystalline CuCoOx with abundant oxygen vacancies

IF 3.9 3区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Research & Design Pub Date : 2025-09-28 DOI:10.1016/j.cherd.2025.09.045

Fei Yan , Luao Wu , Yanxin Quan , Wenhui You , Ping Li , Lina Wei , Guangle Zhou , Lidong Wang

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Abstract

In this study, low-crystalline CuCoO_x with abundant oxygen vacancies (O_v) were prepared by hydrothermal-calcination method using ZIF-67 as the precursor. Abundant O_v in the catalyst enhanced the activation of PMS for bisphenol A (BPA) degradation. The optimum catalyst Cu₁Co₁O_x-2 completely removed BPA with a high rate constant of 0.544 min⁻¹, and it remained high activity in a wide pH range of 3–11. EPR analysis, electrochemical tests and quenching experiments revealed that the Cu₁Co₁O_x-2/PMS system degraded BPA via radical (SO₄^•−, •OH, O₂^•−), and non-radical (¹O₂, electron trasfer) pathways, with O₂^•− playing a predominant role. The synergistic effect between O_v and the bimetal synergy in the catalysts is the key for enhancing PMS activation. DFT analysis confirmed that the surface O_v of Cu₁Co₁O_x-2 enhanced the chemisorption of PMS on neighboring cobalt ions and facilitated the cleavage of the O-O bond of PMS. In addition, O_v enhanced the interfacial charge transfer to PMS, hence boosting PMS activation with a lower energy barrier. This method is useful for eliminating refractory organic pollutants in water.

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zif -67衍生低晶富氧空位CuCoOx高效去除有机污染物的过氧单硫酸盐活化研究

本研究以ZIF-67为前驱体，采用水热煅烧法制备了具有丰富氧空位（Ov）的低晶CuCoOx。催化剂中丰富的Ov增强了PMS降解双酚A （BPA）的活性。最佳催化剂Cu1Co1Ox-2完全去除BPA，速率常数为0.544 min−1，且在3 ~ 11的较宽pH范围内仍保持较高的活性。EPR分析、电化学测试和淬火实验表明，cu1co1x -2/PMS体系通过自由基（SO4•−、•OH、O2•−）和非自由基（1O2、电子转移）途径降解BPA，其中O2•−起主导作用。Ov与催化剂中的双金属协同作用是提高PMS活性的关键。DFT分析证实，Cu1Co1Ox-2的表面Ov增强了PMS对邻近钴离子的化学吸附，促进了PMS O-O键的断裂。此外，Ov增强了界面电荷向PMS的转移，从而以较低的能垒促进了PMS的活化。该方法可用于去除水中难降解的有机污染物。

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来源期刊

Chemical Engineering Research & Design 工程技术-工程：化工

CiteScore

6.10

自引率

7.70%

发文量

623

审稿时长

42 days

期刊介绍： ChERD aims to be the principal international journal for publication of high quality, original papers in chemical engineering. Papers showing how research results can be used in chemical engineering design, and accounts of experimental or theoretical research work bringing new perspectives to established principles, highlighting unsolved problems or indicating directions for future research, are particularly welcome. Contributions that deal with new developments in plant or processes and that can be given quantitative expression are encouraged. The journal is especially interested in papers that extend the boundaries of traditional chemical engineering.