Engineering Electron-Rich Sites on CoSe2-x Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation

doi:10.1021/acs.analchem.1c04785

	Engineering Electron-Rich Sites on CoSe2-x Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation
	Chen, Shi-Hua 1,2; Song, Zong-Yin 1,2; Xiao, Xiang-Yu 1,2; Huang, Hong-Qi 3,4; Yang, Yuan-Fan 1,2; Li, Pei-Hua 1; Yang, Meng 1; Huang, Xing-Jiu 1,2
刊名	ANALYTICAL CHEMISTRY
	2022-02-01
ISSN号	0003-2700
DOI	10.1021/acs.analchem.1c04785
通讯作者	Li, Pei-Hua(peihuali@issp.ac.cn) ; Yang, Meng(myang@iim.ac.cn) ; Huang, Xing-Jiu(xingjiuhuang@iim.ac.cn)
英文摘要	Vacancy and doping engineering are promising pathways to improve the electrocatalytic ability of nanomaterials for detecting heavy metal ions. However, the effects of the electronic structure and the local coordination on the catalytic performance are still ambiguous. Herein, cubic selenium vacancyrich CoSe2 (c-CoSe2-x) and P-doped orthorhombic CoSe2-x (o-CoSe2-x vertical bar P) were designed via vacancy and doping engineering. An o-CoSe2-x vertical bar P-modified glass carbon electrode (o-CoSe2-x vertical bar P/GCE) acquired a high sensitivity of 1.11 mu A ppb(-1) toward As(III), which is about 40 times higher than that of c-CoSe2-x, outperforming most of the reported nanomaterial-modified glass carbon electrodes. Besides, o-CoSe2-x vertical bar P/GCE displayed good selectivity toward As(III) compared with other divalent heavy metal cations, which also exhibited excellent stability, repeatability, and practicality. Xray absorption fine structure spectroscopy and density functional theory calculation demonstrate that electrons transferred from Co and Se to P sites through Co-P and Se-P bonds in o-CoSe2-x vertical bar P. P sites obtained plentiful electrons to form active centers, which also had a strong orbital coupling with As(III). In the detection process, As(III) was bonded with P and reduced by the electron-rich sites in o-CoSe2-x vertical bar P, thus acquiring a reinforced electrochemical sensitivity. This work provides an in-depth understanding of the influence of the intrinsic physicochemical properties of sensitive materials on the behavior of electroanalysis, thus offering a direct guideline for creating active sites on sensing interfaces.
资助项目	National Natural Science Foundation of China[21735005] ; National Natural Science Foundation of China[U1932119] ; Natural Science Foundation of Anhui Province[2008085QB79] ; China National Post-doctoral Program for Innovative Talents[BX2021317] ; China Postdoctoral Science Foundation[2019M652220] ; National Key Basic Research Program of China[2017YFA0403402] ; CASHIPS Director's Fund[YZJJ2022QN26]
WOS关键词	ANODIC-STRIPPING VOLTAMMETRY
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000757792500001
资助机构	National Natural Science Foundation of China ; Natural Science Foundation of Anhui Province ; China National Post-doctoral Program for Innovative Talents ; China Postdoctoral Science Foundation ; National Key Basic Research Program of China ; CASHIPS Director's Fund
内容类型	期刊论文
源URL	[http://ir.hfcas.ac.cn:8080/handle/334002/127766]
专题	中国科学院合肥物质科学研究院
通讯作者	Li, Pei-Hua; Yang, Meng; Huang, Xing-Jiu
作者单位	1.Chinese Acad Sci, Inst Solid State Phys, Key Lab Environm Opt & Technol, Environm Mat & Pollut Control Lab,HFIPS, Hefei 230031, Peoples R China 2.Univ Sci & Technol China, Dept Mat Sci & Engn, Hefei 230026, Peoples R China 3.Anhui Univ, Inst Phys Sci, Hefei 230039, Peoples R China 4.Anhui Univ, Inst Informat Technol, Hefei 230039, Peoples R China
推荐引用方式 GB/T 7714	Chen, Shi-Hua,Song, Zong-Yin,Xiao, Xiang-Yu,et al. Engineering Electron-Rich Sites on CoSe2-x Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation[J]. ANALYTICAL CHEMISTRY,2022.
APA	Chen, Shi-Hua.,Song, Zong-Yin.,Xiao, Xiang-Yu.,Huang, Hong-Qi.,Yang, Yuan-Fan.,...&Huang, Xing-Jiu.(2022).Engineering Electron-Rich Sites on CoSe2-x Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation.ANALYTICAL CHEMISTRY.
MLA	Chen, Shi-Hua,et al."Engineering Electron-Rich Sites on CoSe2-x Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation".ANALYTICAL CHEMISTRY (2022).