期刊
APPLIED CATALYSIS B-ENVIRONMENTAL
卷 300, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.apcatb.2021.120722
关键词
High-valent cobalt-oxo species; Hydroxyl radical; 18O-isotope labeling; Substrate and concentration-dependent; oxidation
资金
- National Natural Science Foundation of China [21776223, 52170091]
- National Key R&D Program of China [2018YFC1903202]
The overlooked role of high-valent cobalt-oxo species (Co(IV)) in the Co(II)/peroxymonosulfate (PMS) process has been revealed recently, showing that Co(IV) can trigger hydroxyl radical (center dot OH) formation and heavily influence the distribution of oxidized products of PMSO. The oxidative contribution of Co(IV) and center dot OH on organic degradation is specifically dependent on the type and concentration of the substrate. This study provides deeper insights into the evolution pathway of center dot OH mediated by Co(IV) species and enriches understandings on the collaborative oxidation mechanism in Co(IV)-involved processes.
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 (center dot 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 center dot OH was triggered by Co(IV) species. Density functional theory calculation demonstrated that Co(IV) initiated center dot OH formation via oxo ligand protonation-induced valence tautomerization. Moreover, the oxidative contribution of Co(IV) and center dot 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 center dot OH mediated by Co(IV) species and enriched the understandings on the collaborative oxidation mechanism in Co(IV)-involved processes.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据