{"title":"Unraveling the Fundamentals of Axial Coordination FeN4+1 Sites Regulating the Peroxymonosulfate Activation for Fenton-Like Activity","authors":"Sijia Jin, Wenxian Tan, Xiaofeng Tang, Mengxuan Li, Xinyi Yu, Haiyan Zhang, Shuang Song, Tao Zeng","doi":"10.1002/smll.202405012","DOIUrl":null,"url":null,"abstract":"Precise modulation of the axial coordination microenvironment in single-atom catalysts (SACs) to enhance peroxymonosulfate (PMS) activation represents a promising yet underexplored approach. This study introduces a pyrolysis-free strategy to fabricate SACs with well-defined axial-FeN<sub>4+1</sub> coordination structures. By incorporating additional out-of-plane axial nitrogen into well-defined FeN<sub>4</sub> active sites within a planar, fully conjugated polyphthalocyanine framework, FeN<sub>4+1</sub> configurations are developed that significantly enhance PMS activation. The axial-FeN<sub>4+1</sub> catalyst excelled in activating PMS, with a high bisphenol A (BPA) degradation rate of 2.256 min<sup>−1</sup>, surpassing planar-FeN<sub>4</sub>/PMS systems by 6.8 times. Theoretical calculations revealed that the axial coordination between N and the Fe sites forms an optimized axial FeN<sub>4+1</sub> structure, disrupting the electron distribution symmetry of Fe and optimizing the electron distribution of the Fe 3d orbital (increasing the d-band center from −1.231 to −0.432 eV). Consequently, this led to an enhanced perpendicular adsorption energy of PMS from −1.79 to −1.82 eV and reduced energy barriers for the formation of the key reaction intermediate (O*) that generates <sup>1</sup>O<sub>2</sub>. This study provides new insights into PMS activation through the axial coordinated engineering of well-defined SACs in water purification processes.","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/smll.202405012","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Precise modulation of the axial coordination microenvironment in single-atom catalysts (SACs) to enhance peroxymonosulfate (PMS) activation represents a promising yet underexplored approach. This study introduces a pyrolysis-free strategy to fabricate SACs with well-defined axial-FeN4+1 coordination structures. By incorporating additional out-of-plane axial nitrogen into well-defined FeN4 active sites within a planar, fully conjugated polyphthalocyanine framework, FeN4+1 configurations are developed that significantly enhance PMS activation. The axial-FeN4+1 catalyst excelled in activating PMS, with a high bisphenol A (BPA) degradation rate of 2.256 min−1, surpassing planar-FeN4/PMS systems by 6.8 times. Theoretical calculations revealed that the axial coordination between N and the Fe sites forms an optimized axial FeN4+1 structure, disrupting the electron distribution symmetry of Fe and optimizing the electron distribution of the Fe 3d orbital (increasing the d-band center from −1.231 to −0.432 eV). Consequently, this led to an enhanced perpendicular adsorption energy of PMS from −1.79 to −1.82 eV and reduced energy barriers for the formation of the key reaction intermediate (O*) that generates 1O2. This study provides new insights into PMS activation through the axial coordinated engineering of well-defined SACs in water purification processes.
期刊介绍:
Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments.
With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology.
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