A nonradical oxidation-based peroxymonosulfate (PMS) activation is an attractive process for pollutant elimination. Herein, a dual-metal-organic framework (MOF) assisted strategy to construct magnetic Fe-Mn oxycarbide anchored on N-doped carbon (FeMn@NC) was proposed for PMS activation. It was found that FeMn@NC-800 displayed superior activity than other comparable counterparts, with nearly 100 % degradation of sulfamethazine (SMZ) within 30 min. Electron paramagnetic resonance and quenching tests revealed that nonradical oxidation (O and high-valent metal-oxo species) dominated the SMZ degradation process. Experimental and theoretical calculations demonstrated that FeMn oxycarbide preferred adsorbing the terminal O of PMS, which could improve the PMS oxidization to produce SO, further generating O. Moreover, dual active sites could lower the energy barrier to cleave the O−O bond of PMS to form high-valent FeMnO species. The present study provided a clue to rationally design high-performance heterogeneous catalysts and proposed a novel nonradical-based catalytic oxidation for environmental cleaning.

中文翻译：

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锚定在氮掺杂碳上的铁锰碳氧化物增强类芬顿催化：高价金属氧物种和单线态氧的重要性

基于非自由基氧化的过一硫酸盐（PMS）活化是一种有吸引力的污染物消除过程。在此，提出了一种双金属有机框架（MOF）辅助策略来构建锚定在氮掺杂碳上的磁性铁锰碳氧化物（FeMn@NC）用于PMS活化。结果发现，FeMn@NC-800 比其他同类产品表现出更优异的活性，磺胺二甲嗪 (SMZ) 在 30 分钟内几乎 100% 降解。电子顺磁共振和猝灭测试表明，非自由基氧化（O 和高价金属氧物种）在 SMZ 降解过程中占主导地位。实验和理论计算表明，FeMn碳氧化物优先吸附PMS的末端O，这可以促进PMS氧化产生SO，进一步生成O。此外，双活性位点可以降低能量势垒，将PMS的O−O键裂解为形成高价 FeMnO 物种。本研究为合理设计高性能多相催化剂提供了线索，并提出了一种用于环境清洁的新型非自由基催化氧化。