Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling

doi:10.1021/acscatal.0c02952

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	Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling
	Lian, Zan 1,2; Si, Chaowei 1,2; Jan, Faheem 1,2; Yang, Min 1,2; Li, Bo 1
刊名	ACS CATALYSIS
	2020-12-04
卷号	10 期号:23 页码:14006-14014
关键词	oxidative dehydrogenation carbon catalysis microkinetic modeling radical reaction reaction mechanism density functional theory
ISSN号	2155-5435
DOI	10.1021/acscatal.0c02952
通讯作者	Li, Bo(boli@imr.ac.cn)
英文摘要	As metal-free catalysts with great potential for widespread application, nanostructured carbon materials have excellent performance comparable to traditional metal oxide catalysts in the oxidative dehydrogenation (ODH) of alkanes. Unlike the mature narrations of the mechanism on the metal catalyst, the mechanism of ODH on the nanocarbon catalyst is still disputable and inconclusive. In this work, density functional theory (DFT) calculation and microkinetic modeling (MKM) are combined to provide unique insights into the mechanism. Four possible mechanisms were studied, which are Eley-Rideal (ER), Langmuir-Hinshelwood (LH), and Mars-van Krevelen (MvK), together with the reactions between weakly adsorbed species and radicals. The simulation clearly identified the mechanism of the reaction that the ER pathway is more likely than both LH and MvK pathways under various conditions. Carbonyl groups are the main active sites for the first hydrogen abstraction of ethylbenzene. On the other hand, the hydrogen abstraction from intermediate hydrocarbons (such as C6H5CHCH3 center dot) by O-2* and HO2 center dot yields a significant contribution to the total reaction rate under certain conditions. The reaction is first-order in ethylbenzene and zero-order in O-2 when the ratio of reactants nears stoichiometry. Moreover, the defective site does not affect the intrinsic catalytic performance. The defective site is subsequently transformed into the carbonyl group at the steady state and thus increases the number of active sites. This study provides a decisive description of the mechanism of ODH on nanocarbon catalysts under various reaction conditions and sheds light on design of the catalyst and optimization of reaction conditions.
资助项目	National Natural Science Foundation of China[21573255] ; Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science ; State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC) ; Special Program for Applied Research on Super Computation of the NSFC Guangdong Joint Fund[U1501501]
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000598140200024
资助机构	National Natural Science Foundation of China ; Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science ; State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC) ; Special Program for Applied Research on Super Computation of the NSFC Guangdong Joint Fund
内容类型	期刊论文
源URL	[http://ir.imr.ac.cn/handle/321006/158945]
专题	金属研究所_中国科学院金属研究所
通讯作者	Li, Bo
作者单位	1.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Liaoning, Peoples R China 2.Univ Sci & Technol China, Sch Mat Sci & Engn, Shenyang 110016, Peoples R China
推荐引用方式 GB/T 7714	Lian, Zan,Si, Chaowei,Jan, Faheem,et al. Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling[J]. ACS CATALYSIS,2020,10(23):14006-14014.
APA	Lian, Zan,Si, Chaowei,Jan, Faheem,Yang, Min,&Li, Bo.(2020).Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling.ACS CATALYSIS,10(23),14006-14014.
MLA	Lian, Zan,et al."Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling".ACS CATALYSIS 10.23(2020):14006-14014.