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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
Source PublicationACS CATALYSIS
ISSN2155-5435
Volume7Issue:6Pages:3779-3785
AbstractTo 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.
description.department[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
KeywordNanodiamond Dehydrogenation Isobutane Dft Sp(2)@Sp(3) Core-shell
Subject AreaChemistry, Physical
Funding OrganizationNSFC [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)
Indexed BySCI
Language英语
Document Type期刊论文
Identifierhttp://ir.imr.ac.cn/handle/321006/78106
Collection中国科学院金属研究所
Corresponding AuthorLi, B; Su, DS (reprint author), Chinese Acad Sci, Shenyang Natl Lab Mat Sci, Inst Met Res, Shenyang 110016, Liaoning, Peoples R China.
Recommended Citation
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.
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