| 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+ | |
| Department | 固体润滑国家重点实验室 |
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)
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| The second department | 空间润滑材料组 |
| 2013 | |
| Source Publication | The Journal of Physical Chemistry A
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| ISSN | 1089-5639 |
| Volume | 117Issue:36Pages:8843-8854 |
| Abstract | 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. |
| Subject Area | 材料科学与物理化学 |
| DOI | 10.1021/jp4050447 |
| Funding Organization | 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 |
| Indexed By | SCI |
| If | 2.775 |
| Language | 英语 |
| compositor | 第一作者单位 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/4223 |
| Collection | 固体润滑国家重点实验室（LSL） |
| Corresponding Author | Guo ZG(郭志光) |
| Affiliation | 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 |
| Recommended Citation 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. |
| Files in This Item: | ||||||
| File Name/Size | DocType | Version | Access | License | ||
| jp4050447.pdf（1402KB） | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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