Chemical Origin of Termination-Functionalized MXenes: Ti3C2T2 as a Case Study

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	Chemical Origin of Termination-Functionalized MXenes: Ti3C2T2 as a Case Study
	Hu, Tao; Li, Zhaojin; Hu, Minmin; Wang, Jiemin; Hu, Qingmiao; Li, Qingzhong; Wang, Xiaohui; Wang, XH (reprint author), Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua Rd, Shenyang 110016, Liaoning, Peoples R China.
	2017-09-07
发表期刊	AMER CHEMICAL SOC
ISSN	1932-7447
卷号	121 期号:35 页码:19254-19261
摘要	MXenes represent a burgeoning family of two-dimensional (2D) functional materials with a variety of applications that highly rely on termination mediated surface functionalization, but the understanding of termination is limited. Here, we take Ti3C2T2 (T = O, F, OH, and H) as an example of MXenes, to demonstrate how termination stabilizes the Ti3C2 monolayer matrix by saturating the nonbonding valence electrons of the surface Ti atom by the low-energy orbitals of the termination. This is achieved by orbitally resolved density of states analysis by simply yet efficiently manipulating the internal coordination of the octahedral crystal field to match exactly the Cartesian coordination. Highly degenerate 3d orbitals of surface Ti split in such a way that it exhibits pseudogaps whose widths predict a stability order Ti3C2O2 > Ti3C2F2 > Ti3C2(OH)(2) > Ti3C2H2 > Ti3C2, consistent with Bader charge analysis, thermodynamic calculations, and experimental results. This new criterion could have implications in the general context of ubiquitous termination phenomena of MXenes and other relevant termination-functionalized 2D materials.; MXenes represent a burgeoning family of two-dimensional (2D) functional materials with a variety of applications that highly rely on termination mediated surface functionalization, but the understanding of termination is limited. Here, we take Ti3C2T2 (T = O, F, OH, and H) as an example of MXenes, to demonstrate how termination stabilizes the Ti3C2 monolayer matrix by saturating the nonbonding valence electrons of the surface Ti atom by the low-energy orbitals of the termination. This is achieved by orbitally resolved density of states analysis by simply yet efficiently manipulating the internal coordination of the octahedral crystal field to match exactly the Cartesian coordination. Highly degenerate 3d orbitals of surface Ti split in such a way that it exhibits pseudogaps whose widths predict a stability order Ti3C2O2 > Ti3C2F2 > Ti3C2(OH)(2) > Ti3C2H2 > Ti3C2, consistent with Bader charge analysis, thermodynamic calculations, and experimental results. This new criterion could have implications in the general context of ubiquitous termination phenomena of MXenes and other relevant termination-functionalized 2D materials.
部门归属	[hu, tao ; li, zhaojin ; hu, minmin ; wang, jiemin ; hu, qingmiao ; wang, xiaohui] chinese acad sci, inst met res, shenyang natl lab mat sci, 72 wenhua rd, shenyang 110016, liaoning, peoples r china ; [hu, tao ; li, zhaojin] univ chinese acad sci, beijing 100049, peoples r china ; [hu, minmin] univ sci & technol china, sch mat sci & engn, hefei 230026, anhui, peoples r china ; [li, qingzhong] yantai univ, sch chem & chem engn, lab theoret & computat chem, yantai 264005, peoples r china
学科领域	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
资助者	Youth Innovation Promotion Association, Chinese Academy of Sciences (CAS) [2011152]; Shenyang National Laboratory for Materials Science, Institute of Metal Research, CAS [2017RP06]; Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund
收录类别	SCI
语种	英语
WOS记录号	WOS:000410597600032
引用统计	被引频次：232[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/79103
专题	中国科学院金属研究所
通讯作者	Wang, XH (reprint author), Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua Rd, Shenyang 110016, Liaoning, Peoples R China.
推荐引用方式 GB/T 7714	Hu, Tao,Li, Zhaojin,Hu, Minmin,et al. Chemical Origin of Termination-Functionalized MXenes: Ti3C2T2 as a Case Study[J]. AMER CHEMICAL SOC,2017,121(35):19254-19261.
APA	Hu, Tao.,Li, Zhaojin.,Hu, Minmin.,Wang, Jiemin.,Hu, Qingmiao.,...&Wang, XH .(2017).Chemical Origin of Termination-Functionalized MXenes: Ti3C2T2 as a Case Study.AMER CHEMICAL SOC,121(35),19254-19261.
MLA	Hu, Tao,et al."Chemical Origin of Termination-Functionalized MXenes: Ti3C2T2 as a Case Study".AMER CHEMICAL SOC 121.35(2017):19254-19261.