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High-valent cobalt-oxo species triggers hydroxyl radical for collaborative environmental decontamination
Applied Catalysis B: Environment and Energy ( IF 20.2 ) Pub Date : 2021-09-20 , DOI: 10.1016/j.apcatb.2021.120722
Yang Zong 1 , Hua Zhang 1 , Xiaomeng Zhang 1 , Wen Liu 2 , Longqian Xu 1 , Deli Wu 1, 3
Affiliation  

The overlooked role of high-valent cobalt-oxo species (Co(IV)) in the Co(II)/peroxymonosulfate (PMS) process was uncovered recently using methyl phenyl sulfoxide (PMSO) as the probe. Herein, we further interestingly found that Co(IV) could trigger hydroxyl radical (OH) formation, resulting in the oxidized products distribution of PMSO heavily relied on the relative concentration of PMSO. More significantly, the generation of a series of 18O-labeled hydroxylated products (i.e., hydroxylated methyl phenyl sulfone, nitrobenzene and 4-nitrobenzoic acid) in H218O conclusively verified that OH was triggered by Co(IV) species. Density functional theory calculation demonstrated that Co(IV) initiated OH formation via oxo ligand protonation-induced valence tautomerization. Moreover, the oxidative contribution of Co(IV) and OH on organic degradation was specifically dependent on the type and concentration of the substrate. This study provided deeper insights into the evolution pathway of OH mediated by Co(IV) species and enriched the understandings on the collaborative oxidation mechanism in Co(IV)-involved processes.



中文翻译:

高价钴-氧物种触发羟基自由基用于协同环境净化

最近使用甲基苯基亚砜(PMSO)作为探针发现了高价钴氧物种(Co(IV))在 Co(II)/过硫酸盐(PMS)过程中被忽视的作用。在此,我们进一步有趣地发现,Co(IV) 可以触发羟基自由基 ( OH) 的形成,导致 PMSO 的氧化产物分布严重依赖于 PMSO 的相对浓度。更重要的是,在 H 2 18 O 中生成的一系列18 O 标记的羟基化产物(即羟基化甲基苯砜、硝基苯和 4-硝基苯甲酸)最终证实了 OH 是由 Co(IV) 物种触发的。密度泛函理论计算表明 Co(IV) 引发了通过氧代配体质子化诱导的价互变异构化形成 OH。此外,Co(IV) 和 OH 对有机降解的氧化作用具体取决于底物的类型和浓度。该研究为Co(IV)物种介导的 OH的演化途径提供了更深入的见解,并丰富了对Co(IV)相关过程中协同氧化机制的理解。

更新日期:2021-09-24
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