In conventional studies, radicals and nonradicals were often considered independent mechanisms for organic pollutant oxidation, with their potential interaction between radicals and nonradicals largely overlooked in Fenton-like reactions. Herein, Cu-Co3O4 catalysts (x wt% Cu-Co3O4/OVs) featuring bifunctional bonding centers were fabricated, which enabled simultaneous co-capture of electron-rich contaminants and peroxymonosulfate (PMS) at their interfaces. The optimized 0.75 wt% Cu-Co3O4/OVs demonstrated exceptional efficiencies in degrading diverse micropollutants through synergistic oxidation pathways involving radicals and nonradical electron transfer process (ETP). Significantly, we found the unique dual electron migration pathways for PMS activation during synergistic oxidation process: besides the electron donation from Co centers, electron could be migrated via ETP from micropollutants to Co sites via heteroatomic Cu, serving as additional electron source for assisting PMS activation. In addition, synergistic oxidation pathways not only enhanced the generation of reactive species but also improved their utilization efficiency by shortening the migration distance of radicals. Such system exhibited remarkable long-term stability (up to 16 h) in wastewater treatment, with its environmental applicability further validated through life cycle assessment and bio-experiments. This work uncovered a previously unrecognized synergistic interaction between radical and nonradical pathways, offering new insights into the interfacial radical-mediated oxidation behavior for advanced wastewater remediation.

中文翻译：

---

揭示非自由基电子供体途径在过氧一硫酸盐活化中促进界面自由基产生的作用

在常规研究中，自由基和非自由基通常被认为是有机污染物氧化的独立机制，它们在自由基和非自由基之间的潜在相互作用在 Fenton 样反应中在很大程度上被忽视了。在此，制备了具有双功能键合中心的 Cu-Co3O4 催化剂 （x wt% Cu-Co3O4/OVs），使其能够在它们的界面上同时共捕获富电子污染物和过氧一硫酸盐 （PMS）。优化的 0.75 wt% Cu-Co3O4/OVs 在通过涉及自由基和非自由基电子转移过程 （ETP） 的协同氧化途径降解各种微污染物方面表现出卓越的效率。值得注意的是，我们发现了协同氧化过程中 PMS 激活的独特双电子迁移途径：除了来自 Co 中心的电子捐赠外，电子还可以通过 ETP 通过杂原子 Cu 从微污染物迁移到 Co 位点，作为辅助 PMS 激活的额外电子源。此外，协同氧化途径不仅促进了反应性物质的生成，而且通过缩短自由基的迁移距离提高了其利用效率。该系统在废水处理中表现出显著的长期稳定性（长达 16 小时），其环境适用性通过生命周期评估和生物实验进一步验证。这项工作揭示了自由基和非自由基途径之间以前未被认识的协同相互作用，为高级废水修复的界面自由基介导的氧化行为提供了新的见解。