通过在活性 Co3O4 中加入氧化还原惰性镁,异常改进过乙酸活化,超快去除有机化合物

Xiaoyang Li, Jiahang Liu, Yingying Chu, Mengying Qian, Zhichao Yang, Weiming Zhang
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引用次数: 0

摘要

过乙酸(PAA)越来越多地用于水净化的高级氧化工艺(AOPs)中,但对高效、低成本活化剂的需求仍然十分迫切。在这里,我们通过在氧化还原活性 CoO 中加入氧化还原惰性镁物种(MgCoO),构建了丰富的氧空位(OV),通过 PAA 活化实现了磺胺甲噁唑(SMX)的超快速降解。MgCoO/PAA 系统在 3 分钟内成功降解了 SMX,其去除率是 CoO/PAA 系统的 154.8 倍,甚至超过了之前报道的单原子催化剂。确定的主要活性物种是乙酰过氧自由基(CHC(O)OO-),Co-oxo 是产生 O 标记砜类化合物的次要活性物种。我们提出了一种新的机制,即氧化还原惰性镁物种同时加强了 PAA 的吸附和活化。掺入镁后表面羟基的丰富提高了与 PAA 结合的亲和力。同时,Co 平均价态的降低和电子传递能力的增强促进了 PAA 的活化。这项研究深入了解了 PAA-AOPs 中氧化还原惰性碱土金属的作用。
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Unusually improved peracetic acid activation for ultrafast organic compound removal through redox-inert Mg incorporation into active Co3O4
Peracetic acid (PAA) is increasingly used in advanced oxidation processes (AOPs) for water purification, yet there remains a critical need for highly-efficient and low-cost activators. Here, we constructed abundant oxygen vacancies (OVs) into redox-active CoO by incorporating redox-inert Mg species (MgCoO), achieving ultrafast degradation of sulfamethoxazole (SMX) via PAA activation. The MgCoO/PAA system successfully degraded SMX within 3 min, with a removal rate 154.8 times higher than the CoO/PAA system, surpassing even previously reported single-atom catalysts. The primary active species identified was the acetylperoxyl radical (CHC(O)OO•), with Co-oxo acting as a secondary active species that produced O-labeled sulfone compounds. We proposed a novel mechanism involving redox-inert Mg species that simultaneously strengthened PAA adsorption and activation. The enriched surface hydroxyl groups after Mg incorporation elevated the affinity for PAA binding. Meanwhile, the reduced Co average valence state and enhanced electron transfer capability facilitated PAA activation. This study offers an in-depth knowledge of redox-inert alkaline earth metals in PAA-AOPs.
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