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Nitrilotriacetic acid-assisted Mn(II) activated periodate for rapid and long-lasting degradation of carbamazepine: The importance of Mn(IV)-oxo species
Water Research ( IF 12.8 ) Pub Date : 2023-05-31 , DOI: 10.1016/j.watres.2023.120156
Yishi Wang 1 , Wei Qiu 1 , Xiaohui Lu 2 , Xiaoqun Zhou 1 , Haochen Zhang 1 , Xiuxue Gong 3 , Baocai Gong 3 , Jun Ma 1
Affiliation  

Periodate-based (PI, IO4) oxidation processes for pollutant elimination have gained increased attention in recent years. This study shows that nitrilotriacetic acid (NTA) can assist trace Mn(II) in activating PI for fast and long-lasting degradation of carbamazepine (CBZ) (100% degradation in 2 min). PI can oxidize Mn(II) to permanganate(MnO4, Mn(VII)) in the presence of NTA, which indicates the important role of transient manganese-oxo species. 18O isotope labeling experiments using methyl phenyl sulfoxide (PMSO) as a probe further confirmed the formation of manganese-oxo species. The chemical stoichiometric relationship (PI consumption: PMSO2 generation) and theoretical calculation suggested that Mn(IV)-oxo-NTA species were the main reactive species. The NTA-chelated manganese facilitated direct oxygen transfer from PI to Mn(II)-NTA and prevented hydrolysis and agglomeration of transient manganese-oxo species. PI was transformed completely to stable and nontoxic iodate but not lower-valent toxic iodine species (i.e., HOI, I2, and I). The degradation pathways and mechanisms of CBZ were investigated using mass spectrometry and density functional theory (DFT) calculation. This study provided a steady and highly efficient choice for the quick degradation of organic micropollutants and broadened the perspective on the evolution mechanism of manganese intermediates in the Mn(II)/NTA/PI system.



中文翻译:

次氮基三乙酸辅助 Mn(II) 激活高碘酸盐快速和持久降解卡马西平:Mn(IV)-oxo 物种的重要性

基于高碘酸盐(PI,输入输出4个) 消除污染物的氧化过程近年来受到越来越多的关注。这项研究表明,次氮基三乙酸 (NTA) 可以协助痕量 Mn(II) 激活 PI,从而快速和持久地降解卡马西平 (CBZ)(2 分钟内 100% 降解)。PI可将Mn(II)氧化成高锰酸盐(二氧化锰4个, Mn(VII)) 在 NTA 存在下, 这表明瞬态锰氧物种的重要作用。使用甲基苯基亚砜 (PMSO) 作为探针的18 O 同位素标记实验进一步证实了锰氧物种的形成。化学计量关系(PI 消耗:PMSO 2代)和理论计算表明 Mn(IV)-oxo-NTA 物种是主要的活性物种。NTA 螯合的锰促进了从 PI 到 Mn(II)-NTA 的直接氧转移,并防止了瞬态锰氧物种的水解和团聚。PI 完全转化为稳定且无毒的碘酸盐,但未转化为低价有毒碘物质(即 HOI、I 2和 I -). 使用质谱和密度泛函理论 (DFT) 计算研究了 CBZ 的降解途径和机制。该研究为有机微污染物的快速降解提供了稳定高效的选择,拓宽了Mn(II)/NTA/PI体系中锰中间体演化机制的视角。

更新日期:2023-06-03
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