Revealing the Role of sp(2)@sp(3) Structure of Nanodiamond in Direct Dehydrogenation: Insight from DFT study

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	Revealing the Role of sp(2)@sp(3) Structure of Nanodiamond in Direct Dehydrogenation: Insight from DFT study
	Liu, TianFu; Ali, Sajjad; Li, Bo; Su, Dang Sheng; Li, B; Su, DS (reprint author), Chinese Acad Sci, Shenyang Natl Lab Mat Sci, Inst Met Res, Shenyang 110016, Liaoning, Peoples R China.
	2017-06-01
发表期刊	ACS CATALYSIS
ISSN	2155-5435
卷号	7 期号:6 页码:3779-3785
摘要	To understand the superior performance of nanodiamond (ND) catalyst in dehydrogenation reactions in comparison with other nanostructured carbon catalysts, first principles calculations are performed to study the direct dehydrogenation of isobutane catalyzed by ND catalyst. The NDs form a unique sp(2)@sp(3) core-shell structure because of the diminishment of the surface dangling bond. The calculations show that, in comparison to carbon nanotubes (CNTs), NDs have a much lower activation-barrier of the first C-H bond activation, which is the rate-limiting step in the reaction. Moreover, the complete reaction pathways revealed from the calculations and the adsorption of isobutene further verify the better activity and selectivity of ND catalyst. The investigation of different morphologies, ND sizes, and the presence of surface hydrogens indicates that the sp(2)@sp(3) core shell structure is crucial for the observed excellent reactivity. The Bader charge analysis shows that the oxygen functional groups on ND have less charge than those on CNT, which favors the homolytic cleavage of the C-H bond of isobutane. Moreover, the carbon atoms on ND could accept more charge than their counterparts on CNT, revealing the active role of surface carbon during the C-H bond activation. The current work establishes the relation between the structures of ND catalyst and the catalytic performance of dehydrogenation reactions, which paves the way for further optimization.; To understand the superior performance of nanodiamond (ND) catalyst in dehydrogenation reactions in comparison with other nanostructured carbon catalysts, first principles calculations are performed to study the direct dehydrogenation of isobutane catalyzed by ND catalyst. The NDs form a unique sp(2)@sp(3) core-shell structure because of the diminishment of the surface dangling bond. The calculations show that, in comparison to carbon nanotubes (CNTs), NDs have a much lower activation-barrier of the first C-H bond activation, which is the rate-limiting step in the reaction. Moreover, the complete reaction pathways revealed from the calculations and the adsorption of isobutene further verify the better activity and selectivity of ND catalyst. The investigation of different morphologies, ND sizes, and the presence of surface hydrogens indicates that the sp(2)@sp(3) core shell structure is crucial for the observed excellent reactivity. The Bader charge analysis shows that the oxygen functional groups on ND have less charge than those on CNT, which favors the homolytic cleavage of the C-H bond of isobutane. Moreover, the carbon atoms on ND could accept more charge than their counterparts on CNT, revealing the active role of surface carbon during the C-H bond activation. The current work establishes the relation between the structures of ND catalyst and the catalytic performance of dehydrogenation reactions, which paves the way for further optimization.
部门归属	[liu, tianfu ; ali, sajjad ; li, bo ; su, dang sheng] chinese acad sci, shenyang natl lab mat sci, inst met res, shenyang 110016, liaoning, peoples r china ; [liu, tianfu] univ sci & technol china, sch mat sci & engn, hefei 230026, anhui, peoples r china ; [ali, sajjad] univ chinese acad sci, beijing 100049, peoples r china
关键词	Nanodiamond Dehydrogenation Isobutane Dft Sp(2)@Sp(3) Core-shell
学科领域	Chemistry, Physical
资助者	NSFC [21573255, 21133010, 51221264, 21261160487]; "Strategic Priority Research Program" of the Chinese Academy of Sciences [XDA09030103]; Institute of Metal Research [Y3NBA211A1]; State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC)
收录类别	SCI
语种	英语
WOS记录号	WOS:000402851600005
引用统计	被引频次：35[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/321006/78106
专题	中国科学院金属研究所
通讯作者	Li, B; Su, DS (reprint author), Chinese Acad Sci, Shenyang Natl Lab Mat Sci, Inst Met Res, Shenyang 110016, Liaoning, Peoples R China.
推荐引用方式 GB/T 7714	Liu, TianFu,Ali, Sajjad,Li, Bo,et al. Revealing the Role of sp(2)@sp(3) Structure of Nanodiamond in Direct Dehydrogenation: Insight from DFT study[J]. ACS CATALYSIS,2017,7(6):3779-3785.
APA	Liu, TianFu,Ali, Sajjad,Li, Bo,Su, Dang Sheng,Li, B,&Su, DS .(2017).Revealing the Role of sp(2)@sp(3) Structure of Nanodiamond in Direct Dehydrogenation: Insight from DFT study.ACS CATALYSIS,7(6),3779-3785.
MLA	Liu, TianFu,et al."Revealing the Role of sp(2)@sp(3) Structure of Nanodiamond in Direct Dehydrogenation: Insight from DFT study".ACS CATALYSIS 7.6(2017):3779-3785.