Wang Lei, Cheng Dongle, Zhang Jian, Liu Huaqing, Cao Xiaoqiang, Chen Xinhan, Guo Aiyun, Wang Yanlong, Chen Zhijie
Institute of Yellow River Delta Earth Surface Processes and Ecological Integrity, College of Safety and Environment Engineering, Shandong University of Science and Technology, Qingdao 266590, China.
Institute of Yellow River Delta Earth Surface Processes and Ecological Integrity, College of Safety and Environment Engineering, Shandong University of Science and Technology, Qingdao 266590, China; UNSW Water Research Centre, School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052, Australia.
J Colloid Interface Sci. 2025 Dec;699(Pt 1):138181. doi: 10.1016/j.jcis.2025.138181. Epub 2025 Jun 14.
Copper-based materials-mediated persulfate activation for pollutant degradation has attracted great interest, with copper species playing a crucial role in generating reactive species. However, the mechanism behind copper valence transformation during the catalytic activation of different persulfates, peroxydisulfate (PDS) and peroxymonosulfate (PMS), remains poorly understood. In this study, commercial copper foam (CF) was used as an activator to evaluate the degradation of tetracycline (TC) through different activation pathways, comparing both PDS and PMS systems. The experimental results show that the PMS/CF system achieved a significantly higher TC degradation rate than the PDS/CF system. Quenching experiments, electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and copper species analysis confirmed that the PMS/CF system primarily follows a hydroxyl radical (•OH)-dominated activation mechanism at the Cu/Cu active interface, while the PDS/CF system operates through a non-radical activation pathway mediated by singlet oxygen (O), alongside contributions from superoxide (O) and •OH radicals at the Cu/Cu interface. Additionally, this study offers a detailed comparison of the degradation pathways and toxicity of TC degradation products in both PMS/CF and PDS/CF systems, considering the impact of environmental factors. This research provides valuable insights into the role of different copper species (Cu/Cu/Cu) in persulfate activation, guiding further studies on developing Cu-based catalysts for advanced oxidation processes (AOPs) applications.
铜基材料介导的过硫酸盐活化用于污染物降解已引起广泛关注，其中铜物种在产生活性物种方面起着关键作用。然而，在不同过硫酸盐（过二硫酸盐（PDS）和过一硫酸盐（PMS））催化活化过程中铜价态转变背后的机制仍知之甚少。在本研究中，商业泡沫铜（CF）被用作活化剂，通过不同的活化途径评估四环素（TC）的降解情况，同时比较PDS和PMS体系。实验结果表明，PMS/CF体系实现的TC降解率显著高于PDS/CF体系。淬灭实验、电子顺磁共振（EPR）、X射线光电子能谱（XPS）以及铜物种分析证实，PMS/CF体系在Cu/Cu活性界面主要遵循以羟基自由基（•OH）为主导的活化机制，而PDS/CF体系则通过由单线态氧（O）介导的非自由基活化途径运行，同时在Cu/Cu界面还有超氧阴离子（O）和•OH自由基的贡献。此外，本研究详细比较了PMS/CF和PDS/CF体系中TC降解产物的降解途径和毒性，并考虑了环境因素的影响。该研究为不同铜物种（Cu/Cu/Cu）在过硫酸盐活化中的作用提供了有价值的见解，为进一步开发用于高级氧化过程（AOPs）应用的铜基催化剂的研究提供了指导。
