Methane Activation by Diatomic Molybdenum Carbide Cations
文献类型：期刊论文
| 作者 | Li, Zi-Yu1,2; Yuan, Zhen1,2; Zhao, Yan-Xia1; He, Sheng-Gui1 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2014-04-01 |
| 卷号 | 20期号:14页码:4163-4169 |
| 关键词 | Cc Coupling Density Functional Calculations Mass Spectrometry Methane Activation Molybdenum Carbide |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201304042 |
| 英文摘要 | Metal carbide species have been proposed as a new type of chemical entity to activate methane in both gas-phase and condensed-phase studies. Herein, methane activation by the diatomic cation MoC+ is presented. MoC+ ions have been prepared and mass-selected by a quadrupole mass filter and then allowed to interact with methane in a hexapole reaction cell. The reactant and product ions have been detected by a reflectron time-of-flight mass spectrometer. Bare metal Mo+ and MoC2H2+ ions have been observed as products, suggesting the occurrence of ethylene elimination and dehydrogenation reactions. The branching ratio of the C2H4 elimination channel is much larger than that of the dehydrogenation channel. Density functional theory calculations have been performed to explore in detail the mechanism of the reaction of MoC+ with CH4. The computed results indicate that the ethylene elimination process involves the occurrence of spin conversions in the CC coupling (doubletquartet) and hydrogen atom transfer (quartetsextet) steps. The carbon atom in MoC+ plays a key role in methane activation because it becomes sp(3) hybridized in the initial stages of the ethylene elimination reaction, which leads to much lower energy barriers and more stable intermediates. This study provides insights into the CH bond activation and CC coupling involved in methane transformation over molybdenum carbide-based catalysts. |
| 语种 | 英语 |
| WOS记录号 | WOS:000333447200038 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/51577]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Zhao, Yan-Xia |
| 作者单位 | 1.Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Struct Chem Unstable & Stable Speci, Inst Chem, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, Zi-Yu,Yuan, Zhen,Zhao, Yan-Xia,et al. Methane Activation by Diatomic Molybdenum Carbide Cations[J]. CHEMISTRY-A EUROPEAN JOURNAL,2014,20(14):4163-4169. |
| APA | Li, Zi-Yu,Yuan, Zhen,Zhao, Yan-Xia,&He, Sheng-Gui.(2014).Methane Activation by Diatomic Molybdenum Carbide Cations.CHEMISTRY-A EUROPEAN JOURNAL,20(14),4163-4169. |
| MLA | Li, Zi-Yu,et al."Methane Activation by Diatomic Molybdenum Carbide Cations".CHEMISTRY-A EUROPEAN JOURNAL 20.14(2014):4163-4169. |
入库方式： OAI收割
来源：化学研究所
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