Dinitrogen Fixation and Reduction by Ta3N3H0,1- Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity
文献类型：期刊论文
| 作者 | Zhao, Yue; Cui, Jia-Tong; Wang, Ming; Valdivielso, David Yubero; Fielicke, Andre; Hu, Lian-Rui; Cheng, Xin; Liu, Qjng-Yu; Li, Zi-Yu; He, Sheng-Gui |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2019-08-14 |
| 卷号 | 141期号:32页码:12592-12600 |
| ISSN号 | 0002-7863 |
| DOI | 10.1021/jacs.9b03168 |
| 英文摘要 | Dinitrogen activation and reduction is one of the most challenging and important subjects in chemistry. Herein, we report the N-2 binding and reduction at the well-defined Ta3N3H- and Ta3N3- gas-phase clusters by using mass spectrometry (MS), anion photoelectron spectroscopy (PES), and quantum-chemical calculations. The PES and calculation results show clear evidence that N-2 can be adsorbed and completely activated by Ta3N3H- and Ta3N3- clusters, yielding to the products Ta3N5H- and Ta3N5-, but the reactivity of Ta3N3H- is five times higher than that of the dehydrogenated Ta3N3- clusters. The detailed mechanistic investigations further indicate that a dissociative mechanism dominates the N-2 activation reactions mediated by Ta3N3H- and Ta3N3-; two and three Ta atoms are active sites and also electron donors for the N-2 reduction, respectively. Although the hydrogen atom in Ta3N3H- is not directly involved in the reaction, its very presence modifies the charge distribution and the geometry of Ta3N3H-, which is crucial to increase the reactivity. The mechanisms revealed in this gas-phase study stress the fundamental rules for N-2 activation and the important role of transition metals as active sites as well as the new significant role of metal hydride bonds in the process of N-2 reduction, which provides molecular-level insights into the rational design of tantalum nitride-based catalysts for N-2 fixation and activation or NH3 synthesis. |
| 语种 | 英语 |
| WOS记录号 | WOS:000481563500026 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/82663]  |
| 专题 | 中国科学院化学研究所 |
| 作者单位 | Chinese Acad Sci, Inst Chem, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhao, Yue,Cui, Jia-Tong,Wang, Ming,et al. Dinitrogen Fixation and Reduction by Ta3N3H0,1- Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2019,141(32):12592-12600. |
| APA | Zhao, Yue.,Cui, Jia-Tong.,Wang, Ming.,Valdivielso, David Yubero.,Fielicke, Andre.,...&Ma, Jia-Bi.(2019).Dinitrogen Fixation and Reduction by Ta3N3H0,1- Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,141(32),12592-12600. |
| MLA | Zhao, Yue,et al."Dinitrogen Fixation and Reduction by Ta3N3H0,1- Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141.32(2019):12592-12600. |
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来源：化学研究所
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