Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites

Heterogeneous Fenton has emerged as a profitable solution for contaminant removal via advanced oxidation processes (AOPs). Besides the dominant hydroxyl radicals (HO•), some weaker oxidants, such as ferryl-oxo species (Fe(IV)=O) species, can also be produced during the surface H2O2 activation, but i...

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Autores principales:	Jinling Wang, Shifa Zhong, Yuzhen Wen, Jianan Li, Hualin Wang, Honglai Liu, Changzheng Cui, Ming Gong, Huichun Zhang, Xuejing Yang
Formato:	article
Lenguaje:	EN
Publicado:	Elsevier 2022
Materias:	FeOCl Fenton chemistry Ferryl-oxo Micropollutants Oxidative coupling Chemical engineering TP155-156
Acceso en línea:	https://doaj.org/article/887e310002b9416fb952c72ad6d9d310
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spelling	oai:doaj.org-article:887e310002b9416fb952c72ad6d9d3102021-12-02T05:04:28ZCoupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites2666-821110.1016/j.ceja.2021.100214https://doaj.org/article/887e310002b9416fb952c72ad6d9d3102022-03-01T00:00:00Zhttp://www.sciencedirect.com/science/article/pii/S2666821121001290https://doaj.org/toc/2666-8211Heterogeneous Fenton has emerged as a profitable solution for contaminant removal via advanced oxidation processes (AOPs). Besides the dominant hydroxyl radicals (HO•), some weaker oxidants, such as ferryl-oxo species (Fe(IV)=O) species, can also be produced during the surface H2O2 activation, but its function is not well understood. In this study, we developed a vanadium-etched iron oxychloride (V-FeOCl) catalyst that simultaneously incorporates Fenton-like sites and peroxidase-like (Fe(IV)=O) sites. The derived V-FeOCl material showed 2.8–5.4 times enhancement of the pseudo-first-order rate constant for various recalcitrant organic micropollutants. Most importantly, the activity demonstrated an intriguing induction period for the TOC removal as well as a rocketed kinetics after the induction. This induction period was further attributed to the oxidative coupling of the organic monomers, as revealed by the identification of dimers using UPLC-MS. The coupling intermediates were demonstrated to be more susceptible to HO• radical attack via the high-throughput prediction of the HO• radical rate constants of 94 possible coupling intermediates using machine learning. These findings clarified the key role of Fe(IV)=O in the HO•-based oxidation process and points to a novel coupling-enhanced degradation pathway, which could potentially pave a new avenue of oxidative transformations for catalytic and environmental applications.Jinling WangShifa ZhongYuzhen WenJianan LiHualin WangHonglai LiuChangzheng CuiMing GongHuichun ZhangXuejing YangElsevierarticleFeOClFenton chemistryFerryl-oxoMicropollutantsOxidative couplingChemical engineeringTP155-156ENChemical Engineering Journal Advances, Vol 9, Iss , Pp 100214- (2022)
institution	DOAJ
collection	DOAJ
language	EN
topic	FeOCl Fenton chemistry Ferryl-oxo Micropollutants Oxidative coupling Chemical engineering TP155-156
spellingShingle	FeOCl Fenton chemistry Ferryl-oxo Micropollutants Oxidative coupling Chemical engineering TP155-156 Jinling Wang Shifa Zhong Yuzhen Wen Jianan Li Hualin Wang Honglai Liu Changzheng Cui Ming Gong Huichun Zhang Xuejing Yang Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites
description	Heterogeneous Fenton has emerged as a profitable solution for contaminant removal via advanced oxidation processes (AOPs). Besides the dominant hydroxyl radicals (HO•), some weaker oxidants, such as ferryl-oxo species (Fe(IV)=O) species, can also be produced during the surface H2O2 activation, but its function is not well understood. In this study, we developed a vanadium-etched iron oxychloride (V-FeOCl) catalyst that simultaneously incorporates Fenton-like sites and peroxidase-like (Fe(IV)=O) sites. The derived V-FeOCl material showed 2.8–5.4 times enhancement of the pseudo-first-order rate constant for various recalcitrant organic micropollutants. Most importantly, the activity demonstrated an intriguing induction period for the TOC removal as well as a rocketed kinetics after the induction. This induction period was further attributed to the oxidative coupling of the organic monomers, as revealed by the identification of dimers using UPLC-MS. The coupling intermediates were demonstrated to be more susceptible to HO• radical attack via the high-throughput prediction of the HO• radical rate constants of 94 possible coupling intermediates using machine learning. These findings clarified the key role of Fe(IV)=O in the HO•-based oxidation process and points to a novel coupling-enhanced degradation pathway, which could potentially pave a new avenue of oxidative transformations for catalytic and environmental applications.
format	article
author	Jinling Wang Shifa Zhong Yuzhen Wen Jianan Li Hualin Wang Honglai Liu Changzheng Cui Ming Gong Huichun Zhang Xuejing Yang
author_facet	Jinling Wang Shifa Zhong Yuzhen Wen Jianan Li Hualin Wang Honglai Liu Changzheng Cui Ming Gong Huichun Zhang Xuejing Yang
author_sort	Jinling Wang
title	Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites
title_short	Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites
title_full	Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites
title_fullStr	Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites
title_full_unstemmed	Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites
title_sort	coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (feocl) with dual active sites
publisher	Elsevier
publishDate	2022
url	https://doaj.org/article/887e310002b9416fb952c72ad6d9d310
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Coupling-promoted oxidative degradation of organic micropollutants by iron oxychloride (FeOCl) with dual active sites

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