First-Principles Studies of the Activation of Oxygen Molecule and Its Role in Partial Oxidation of Methane on Boron-Doped Single-Walled Carbon Nanotubes

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	First-Principles Studies of the Activation of Oxygen Molecule and Its Role in Partial Oxidation of Methane on Boron-Doped Single-Walled Carbon Nanotubes
	B. Li; D. S. Su
	2013
发表期刊	Journal of Physical Chemistry C
ISSN	1932-7447
卷号	117 期号:34 页码:17485-17492
摘要	The nanostructured carbon materials have been widely tested as catalyst in a number of chemical reactions. The oxygen functional groups on nanostructured carbon catalyst are believed to be the active sites, for example, in the oxidative dehydrogenation reaction of hydrocarbons. However, the doping is one of the effective ways to tune the properties of nanostructured carbon materials. It will be important to examine the effect of doping on the catalytic properties of oxygen molecule on nanostructured carbon materials. In current work, the dissociation of the oxygen molecule on the boron-doped single-walled carbon nanotube (BSWCNT) and their catalytic properties in the partial oxidation of methane to formaldehyde are investigated by using first-principles calculations. Both defect-free BSWCNT and defective BSWCNT with a monovacancy are studied, and the comparisons between them are made. BSWCNT demonstrates a good ability for the dissociation of oxygen molecule. The favorable binding sites for the dissociated oxygen molecule are the positively charged atoms on BSWCNTs because oxygen molecule itself is negatively charged by obtaining electrons from carbons. The barrier of the oxygen dissociation is 0.88 and 0.12 eV, respectively, for defect-free and defective BSWCNTs. Furthermore, the dissociated oxygen molecule on BSWCNT exhibits the ability to break the C H bond in methane molecule and the dissociated fragments (CH3 and H) bind on the oxygens on BSWCNTs. The C H bond breaking results from the charge abstraction from hydrogen in methane molecule by BSWCNT. The minimum energy path looks similar for both defect-free and defective BSWCNTs, which involves a methyl radical translation after transition state. However, the barrier is smaller by 0.5 eV on defective BSWCNTs and comparable with other catalysts for methane activation. The CH3O on BSWCNT can be further converted to the formaldehyde with the calculated barrier of 1.37 eV. The current study indicates that the boron doping is a promising effective way to optimize the catalytic properties of carbon nanotube catalyst.
部门归属	[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. ; dangsheng@fhi-berlin.mpg.de
关键词	Total-energy Calculations Augmented-wave Method Catalytic Performance Metal-catalysts Basis-set Dehydrogenation Ethylbenzene Chemistry Nitrogen Defects
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/321006/71305
专题	中国科学院金属研究所
推荐引用方式 GB/T 7714	B. Li,D. S. Su. First-Principles Studies of the Activation of Oxygen Molecule and Its Role in Partial Oxidation of Methane on Boron-Doped Single-Walled Carbon Nanotubes[J]. Journal of Physical Chemistry C,2013,117(34):17485-17492.
APA	B. Li,&D. S. Su.(2013).First-Principles Studies of the Activation of Oxygen Molecule and Its Role in Partial Oxidation of Methane on Boron-Doped Single-Walled Carbon Nanotubes.Journal of Physical Chemistry C,117(34),17485-17492.
MLA	B. Li,et al."First-Principles Studies of the Activation of Oxygen Molecule and Its Role in Partial Oxidation of Methane on Boron-Doped Single-Walled Carbon Nanotubes".Journal of Physical Chemistry C 117.34(2013):17485-17492.