Xu Huajie, Zhang Mengyu, Zhang Qian, Wu Junrong, Zhou Xiaofeng, Zhang Jiaojiao, Hao Fuying, Liu Zhaodi, Sheng Liangquan, Tang Yu
Engineering Research Center of Biomass Conversion and Pollution Prevention of Anhui Educational Institutions, School of Chemistry and Materials Engineering, Fuyang Normal University, Fuyang, Anhui, 236037, China.
State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
Angew Chem Int Ed Engl. 2025 Aug 18;64(34):e202509527. doi: 10.1002/anie.202509527. Epub 2025 Jul 2.
Rational modulation of edge active sites in the Fenton-like reaction, utilizing defect engineering to form efficient catalytic activity centers, is a hot topic in the heterogeneous catalysis field, yet the applicability of large-scale manufacturing remains a severe challenge. Herein, a general wet-chemical approach is reported to large-scale prepare porous CoMnO with abundant active edge sites for enhanced peroxymonosulfate (PMS)-based Fenton-like activation without using a template or heat treatment. The obtained Turing-type structure not only can be assembled into spatially restricted domain CoMnO nanoreactors but also greatly facilitates the exposure of active edge sites with oxygen-rich vacancies in promoting PMS adsorption and interfacial charge transfer. The unique CoMnO/PMS system exhibited efficient and stable removal of organic pollutants with dominant nonradical (O) pathways and maintained a degradation rate of 99.8% within 5 min after seven-cycle runs. Moreover, the application prospect of the PMS-based Fenton-like process for large-scale wastewater treatment, including sulfadiazine (SD) antibiotics in real river water and real pharmaceutical wastewater, was demonstrated by the fixed-bed tower reactor and the in-situ floating water treatment device. This work will provide guidance for the development of low-cost and efficient heterogeneous PMS-activation catalysts through rational defect engineering.
利用缺陷工程形成高效催化活性中心，对类芬顿反应中的边缘活性位点进行合理调控，是多相催化领域的一个热门话题，然而大规模制造的适用性仍然是一个严峻挑战。在此，报道了一种通用的湿化学方法，用于大规模制备具有丰富活性边缘位点的多孔CoMnO，以增强基于过一硫酸盐（PMS）的类芬顿活化，而无需使用模板或热处理。所获得的图灵型结构不仅可以组装成空间受限的域CoMnO纳米反应器，而且在促进PMS吸附和界面电荷转移方面极大地促进了富含氧空位的活性边缘位点的暴露。独特的CoMnO/PMS系统表现出高效稳定地去除有机污染物，主要通过非自由基（O）途径，并且在七次循环运行后的5分钟内降解率保持在99.8%。此外，固定床塔式反应器和原位漂浮水处理装置证明了基于PMS的类芬顿工艺在大规模废水处理中的应用前景，包括实际河水中的磺胺嘧啶（SD）抗生素和实际制药废水。这项工作将为通过合理的缺陷工程开发低成本、高效的多相PMS活化催化剂提供指导。
