The first principles studies on the reaction pathway of the oxidative dehydrogenation of ethane on the undoped and doped carbon catalyst

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	The first principles studies on the reaction pathway of the oxidative dehydrogenation of ethane on the undoped and doped carbon catalyst
	S. J. Mao; B. Li; D. S. Su
	2014
发表期刊	Journal of Materials Chemistry A
ISSN	2050-7488
卷号	2 期号:15 页码:5287-5294
摘要	The oxidation dehydrogenation (ODH) of ethane on a carbon catalyst is studied by first principles calculations. From the examination of the ethane chemisorption at the various oxygen functional groups, the ketonic-like groups, diketone and quinone are identified as the active sites. Two different pathways are explored after the first C-H bond breaking in the ethane molecule, which has a barrier of 1.48 eV: (1) the ethyl radical becomes the adsorbed ethoxide and the further forwarding reaction encounters a large barrier, which is not kinetically favorable. (2) The ethyl radical is reoriented and directly activated at the diketone site to form ethylene. Nitrogen and boron doping can effectively alter the reaction pathway. It is found that the barrier of the first C-H bond breaking at the armchair termination is decreased after doping. Also, nitrogen doping makes the intermediate ethoxide less stable, which facilitates a further reaction to ethylene formation. The mechanism of the regeneration of the active sites is different from the one for the metal oxide catalyst. The combination of two neighboring hydroxyls into a water molecule is not feasible. Instead, two routes for active site regeneration on the carbon catalyst are proposed using either the oxygen molecule or the dissociated oxygen atom as the oxidant. The current work gives a detailed description of the whole process of the ODH of ethane on a carbon catalyst. The results from the calculations not only deepen the understanding of the reaction mechanism of ODH of ethane on a carbon catalyst, but also provide valuable insights for the optimization of the carbon catalyst performance in general.
部门归属	[mao, shanjun ; li, bo ; su, dangsheng] chinese acad sci, inst met res, shenyang natl lab mat sci, shenyang 110016, peoples r china. ; su, ds (reprint author), chinese acad sci, inst met res, shenyang natl lab mat sci, 72 wenhua rd, shenyang 110016, peoples r china. ; dssu@imr.ac.cn
关键词	Density-functional Theory Vanadium-oxide Catalysts Total-energy Calculations Augmented-wave Method Selective Oxidation Basis-set N-butane Nanotubes Propane Surface
URL	查看原文
语种	英语
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/72889
专题	中国科学院金属研究所
推荐引用方式 GB/T 7714	S. J. Mao,B. Li,D. S. Su. The first principles studies on the reaction pathway of the oxidative dehydrogenation of ethane on the undoped and doped carbon catalyst[J]. Journal of Materials Chemistry A,2014,2(15):5287-5294.
APA	S. J. Mao,B. Li,&D. S. Su.(2014).The first principles studies on the reaction pathway of the oxidative dehydrogenation of ethane on the undoped and doped carbon catalyst.Journal of Materials Chemistry A,2(15),5287-5294.
MLA	S. J. Mao,et al."The first principles studies on the reaction pathway of the oxidative dehydrogenation of ethane on the undoped and doped carbon catalyst".Journal of Materials Chemistry A 2.15(2014):5287-5294.