Cao Xinqiang, Liu Yang, Yang Fucai, Huang Xianhang, Qiu Wenfeng
South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China.
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China.
J Colloid Interface Sci. 2025 Aug 15;692:137490. doi: 10.1016/j.jcis.2025.137490. Epub 2025 Mar 31.
Mono-metal active sites, with their restricted electron transfer ability, typically lead to lower redox reaction efficiency, which hampers peroxymonosulfate (PMS) activation and reduces antibiotic degradation effectiveness. In this work, a novel nitrogen-doped carbon catalyst with Co-Cu-CuxO interfaces was synthesized by pyrolyzing a Zn-based elliptical two-dimensional template through a Co/Cu bimetallic ion exchange process. The synthesized samples were comprehensively characterized using a range of physicochemical analysis techniques. Furthermore, the catalytic performance was systematically evaluated under varying conditions, including peroxymonosulfate dosage, tetracycline concentration, solution pH, and the influence of co-existing ions and organic matter in water. The results indicated that the optimized 1:1-950 catalyst achieved over 96 % degradation of tetracycline (TC) through PMS activation, with a reaction rate constant (k) of 0.038 min, significantly outperforming both the mono-metal ion exchange group and the non-metal ion exchange group. This improvement was attributed to the synergistic effects of Co(II)/Co(III) and Cu(I)/Cu(II) redox reactions at the Co-Cu-CuxO interfaces. Quenching experiments, electron spin resonance (ESR), and electrochemical analyses revealed that non-radical reactive oxygen species (ROS), such as singlet oxygen (O) and high-valent metal-oxo species (e.g., Cu(III)-oxo and Co(IV)-oxo), played a key role in the degradation process. The degradation pathways for TC were proposed using high-performance liquid chromatography-mass spectrometry (HPLC-MS), and the environmental safety of the catalytic system was confirmed through physiological testing on mung bean growth. This work presents an efficient approach for PMS activation in TC degradation, using nitrogen-doped carbon catalysts with Co-Cu-CuxO interfaces synthesized via bimetallic ion exchange and carbonization strategy, with promising applications in advanced wastewater treatment.
单金属活性位点由于其受限的电子转移能力，通常会导致较低的氧化还原反应效率，这阻碍了过一硫酸盐（PMS）的活化并降低了抗生素降解效果。在本工作中，通过Co/Cu双金属离子交换过程热解锌基椭圆形二维模板，合成了一种具有Co-Cu-CuxO界面的新型氮掺杂碳催化剂。使用一系列物理化学分析技术对合成的样品进行了全面表征。此外，在不同条件下系统评估了催化性能，包括过一硫酸盐用量、四环素浓度、溶液pH值以及水中共存离子和有机物的影响。结果表明，优化后的1:1-950催化剂通过PMS活化实现了超过96%的四环素（TC）降解，反应速率常数（k）为0.038 min，显著优于单金属离子交换组和非金属离子交换组。这种改进归因于Co-Cu-CuxO界面处Co(II)/Co(III)和Cu(I)/Cu(II)氧化还原反应的协同作用。猝灭实验、电子自旋共振（ESR）和电化学分析表明，单线态氧（O）和高价金属氧物种（如Cu(III)-氧和Co(IV)-氧）等非自由基活性氧物种（ROS）在降解过程中起关键作用。使用高效液相色谱-质谱联用（HPLC-MS）提出了TC的降解途径，并通过对绿豆生长的生理测试证实了催化系统的环境安全性。本工作提出了一种利用双金属离子交换和碳化策略合成的具有Co-Cu-CuxO界面的氮掺杂碳催化剂用于TC降解中PMS活化的有效方法，在高级废水处理中具有广阔的应用前景。
