{"title":"从多种金属氧配合物的角度重新审视基于铁(II)/钴(II)的同质芬顿样过程","authors":"Yingxu Gong, Zhonglin Chen, Yining Wu, Aijie Wang, Shengxin Zhao","doi":"10.1021/acs.est.4c03211","DOIUrl":null,"url":null,"abstract":"<p><p>The aqueous Fe<sup>IV</sup>-oxo complex and Fe<sup>III</sup>-peroxy complex (e.g., ligand-assisted or interfacial Fe<sup>III</sup>-hydroperoxo intermediates) have been recognized as crucial reactive intermediates for decontamination in iron-based Fenton-like processes. Intermediates with terminal oxo ligands can undergo the oxygen atom exchange process with water molecules, whereas peroxides are unable to induce such exchanges. Therefore, these distinct metal-oxygen complexes can be distinguished based on the above feature. In this study, we identified previously unknown intermediates with a peroxy moiety and cobalt center that were generated during peroxymonosulfate (PMS) activation via aqueous Co<sup>II</sup> ions under acidic conditions. Results of theoretical calculations and tip-enhanced Raman spectroscopy revealed that the Co<sup>II</sup> ion tended to coordinate with the PMS anion to form a bidentate complex with a tetrahedral structure. These reactive cobalt intermediates were collectively named the Co<sup>II</sup>-PMS* complex. Depending on the inherent characteristics of the target contaminants, the Co<sup>II</sup>-PMS* complex can directly oxidize organic compounds or trigger PMS disproportionation to release hydroxyl radicals and sulfate radicals for collaborative decontamination. This work provides a comparative study between iron- and cobalt-based Fenton-like processes and proposes novel insights from the standpoint of diverse metal-oxygen complexes.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":null,"pages":null},"PeriodicalIF":10.8000,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Revisiting the Iron(II)/Cobalt(II)-Based Homogenous Fenton-like Processes from the Standpoint of Diverse Metal-Oxygen Complexes.\",\"authors\":\"Yingxu Gong, Zhonglin Chen, Yining Wu, Aijie Wang, Shengxin Zhao\",\"doi\":\"10.1021/acs.est.4c03211\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The aqueous Fe<sup>IV</sup>-oxo complex and Fe<sup>III</sup>-peroxy complex (e.g., ligand-assisted or interfacial Fe<sup>III</sup>-hydroperoxo intermediates) have been recognized as crucial reactive intermediates for decontamination in iron-based Fenton-like processes. Intermediates with terminal oxo ligands can undergo the oxygen atom exchange process with water molecules, whereas peroxides are unable to induce such exchanges. Therefore, these distinct metal-oxygen complexes can be distinguished based on the above feature. In this study, we identified previously unknown intermediates with a peroxy moiety and cobalt center that were generated during peroxymonosulfate (PMS) activation via aqueous Co<sup>II</sup> ions under acidic conditions. Results of theoretical calculations and tip-enhanced Raman spectroscopy revealed that the Co<sup>II</sup> ion tended to coordinate with the PMS anion to form a bidentate complex with a tetrahedral structure. These reactive cobalt intermediates were collectively named the Co<sup>II</sup>-PMS* complex. Depending on the inherent characteristics of the target contaminants, the Co<sup>II</sup>-PMS* complex can directly oxidize organic compounds or trigger PMS disproportionation to release hydroxyl radicals and sulfate radicals for collaborative decontamination. This work provides a comparative study between iron- and cobalt-based Fenton-like processes and proposes novel insights from the standpoint of diverse metal-oxygen complexes.</p>\",\"PeriodicalId\":36,\"journal\":{\"name\":\"环境科学与技术\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.8000,\"publicationDate\":\"2024-09-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"环境科学与技术\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.est.4c03211\",\"RegionNum\":1,\"RegionCategory\":\"环境科学与生态学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/9/5 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"ENGINEERING, ENVIRONMENTAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"环境科学与技术","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.est.4c03211","RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/9/5 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"ENGINEERING, ENVIRONMENTAL","Score":null,"Total":0}
Revisiting the Iron(II)/Cobalt(II)-Based Homogenous Fenton-like Processes from the Standpoint of Diverse Metal-Oxygen Complexes.
The aqueous FeIV-oxo complex and FeIII-peroxy complex (e.g., ligand-assisted or interfacial FeIII-hydroperoxo intermediates) have been recognized as crucial reactive intermediates for decontamination in iron-based Fenton-like processes. Intermediates with terminal oxo ligands can undergo the oxygen atom exchange process with water molecules, whereas peroxides are unable to induce such exchanges. Therefore, these distinct metal-oxygen complexes can be distinguished based on the above feature. In this study, we identified previously unknown intermediates with a peroxy moiety and cobalt center that were generated during peroxymonosulfate (PMS) activation via aqueous CoII ions under acidic conditions. Results of theoretical calculations and tip-enhanced Raman spectroscopy revealed that the CoII ion tended to coordinate with the PMS anion to form a bidentate complex with a tetrahedral structure. These reactive cobalt intermediates were collectively named the CoII-PMS* complex. Depending on the inherent characteristics of the target contaminants, the CoII-PMS* complex can directly oxidize organic compounds or trigger PMS disproportionation to release hydroxyl radicals and sulfate radicals for collaborative decontamination. This work provides a comparative study between iron- and cobalt-based Fenton-like processes and proposes novel insights from the standpoint of diverse metal-oxygen complexes.
期刊介绍:
Environmental Science & Technology (ES&T) is a co-sponsored academic and technical magazine by the Hubei Provincial Environmental Protection Bureau and the Hubei Provincial Academy of Environmental Sciences.
Environmental Science & Technology (ES&T) holds the status of Chinese core journals, scientific papers source journals of China, Chinese Science Citation Database source journals, and Chinese Academic Journal Comprehensive Evaluation Database source journals. This publication focuses on the academic field of environmental protection, featuring articles related to environmental protection and technical advancements.