Theoretical Views on Activation of Methane Catalyzed by Hf2+ and Oxidation of CO (x(1)Sigma(+)) by N2O (x(1)Sigma(+)) Catalyzed by HfO2+ and TaO2+

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	Theoretical Views on Activation of Methane Catalyzed by Hf2+ and Oxidation of CO (x(1)Sigma(+)) by N2O (x(1)Sigma(+)) Catalyzed by HfO2+ and TaO2+
	Nian JY(念敬妍)1 ; Tie L(铁璐)1 ; Wang B(王奔)1,2; Guo ZG(郭志光)1,2 ; Guo ZG(郭志光)
刊名	The Journal of Physical Chemistry A
	2013
卷号	117 期号:36 页码:8843-8854
ISSN号	1089-5639
通讯作者	郭志光
英文摘要	The mechanisms of activation of CH₄ catalyzed by ^1/3Hf ²⁺and oxidation of CO by N₂O catalyzed by ^1/3HfO²⁺or ^2/4TaO²⁺ have been investigated using B3LYP level of theory. For the activation of methane, TSR (Two-state reactivity) mechanism has been certified through spin-orbit coupling (SOC) calculation and Landau-Zener-type model. In the vicinity of minimum energy crossing point (MECP), SOC equals 900.23 cm^-1 and probability of inter-system crossing is approximately 0.62. Spin inversion makes the activation barrier decline from 1.63 to 0.57 eV. NBO analysis demonstrates that empty 6s and 5d orbitals of Hf atom play the major role for the activation of C-H bonds. Finally, CH₄ dehydrogenates to produce Hf-CH₂²⁺. For oxidation of CO by N₂O catalyzed by HfO²⁺or TaO²⁺, the covalent bonds between transition metal atoms and oxygen atom restrict the freedom of valence electrons. Therefore, they are all SSR (Single-state reactivity). Oxygen atom is directly extracted during the course of oxygen transfer, and its microscopic essence has been discussed. The detailed kinetic information of two catalytic cycles has been calculated by referencing “energetic span (δE)” model. Finally, TOF (HfO²⁺) / TOF (TaO²⁺) = 2.7 at 298.15 K, which has a good consistency with experimental result.
学科主题	材料科学与物理化学
收录类别	SCI
资助信息	the National Nature Science Foundation of China (Nos. 31070155;11172301;21203217);the “Funds for Distinguished Young Scientists” of Hubei Province (2012FFA002), the cojoint scientific fieldproject, the “Western Light Talent Culture” Project;the “Top Hundred Talents” Program of Chinese Academy of Sciences
语种	英语
WOS记录号	WOS:000330145400037
公开日期	2013-12-02
内容类型	期刊论文
源URL	[http://210.77.64.217/handle/362003/4223]
专题	兰州化学物理研究所_固体润滑国家重点实验室
通讯作者	Guo ZG(郭志光)
作者单位	1.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Solid Lubricat, Lanzhou 730000, Peoples R China 2.Hubei Univ, Key Lab Green Preparat & Applicat Funct Mat, Minist Educ, Wuhan 430062, Peoples R China
推荐引用方式 GB/T 7714	Nian JY,Tie L,Wang B,et al. Theoretical Views on Activation of Methane Catalyzed by Hf2+ and Oxidation of CO (x(1)Sigma(+)) by N2O (x(1)Sigma(+)) Catalyzed by HfO2+ and TaO2+[J]. The Journal of Physical Chemistry A,2013,117(36):8843-8854.
APA	Nian JY,Tie L,Wang B,Guo ZG,&郭志光.(2013).Theoretical Views on Activation of Methane Catalyzed by Hf2+ and Oxidation of CO (x(1)Sigma(+)) by N2O (x(1)Sigma(+)) Catalyzed by HfO2+ and TaO2+.The Journal of Physical Chemistry A,117(36),8843-8854.
MLA	Nian JY,et al."Theoretical Views on Activation of Methane Catalyzed by Hf2+ and Oxidation of CO (x(1)Sigma(+)) by N2O (x(1)Sigma(+)) Catalyzed by HfO2+ and TaO2+".The Journal of Physical Chemistry A 117.36(2013):8843-8854.