Methane activation by heteronuclear diatomic AuRh+ cation: comparison with homonuclear Au2+ and Rh2+
Methane activation by heteronuclear diatomic AuRh+ cation: comparison with homonuclear Au2+ and Rh2+
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异核双原子 AuRh 阳离子活化甲烷：与同核 Au2 和 Rh2 的比较
DOI：
10.1039/c9cp05699h
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发表时间：
2020
影响因子：
3.3
通讯作者：
He Sheng-Gui
中科院分区：
文献类型：
--
作者：
Wang Meng-Meng;Zhao Yan-Xia;Ding Xun-Lei;Li Wei;He Sheng-Gui
不同的过渡金属活化甲烷的能力明显不同，寻找最合适的金属将甲烷直接转化为增值化学品是有吸引力的。本文通过质谱实验和DFT理论分析，对CH 4与Au 2+、AuRh+和Rh 2+的反应进行了比较研究。Au ~（2+）的反应活性最低，能活化甲烷，但只生成H-Au ~（2-CH ~（3+），不释放H ~ 2; Rh ~（2+）的反应活性最高，既能生成卡宾型Rh ~（2-CH ~（2+），又能生成卡宾型H-Rh ~（2-CH ~（2+），释放H ~ 2; AuRh+还具有高反应性，仅与H2生成AuRh-CH 2+，避免了CH 4的过度脱氢。我们的理论结果表明，Rh是负责高的反应性，而Au导致的选择性，这可能是由独特的内在键合性质的金属。
The ability to activate methane differs appreciably for different transition metals, and it is attractive to find the most suitable metal for the direct conversion of methane to value-added chemicals. Herein, we performed a comparative study on the reactions of CH4 with Au2+, AuRh+ and Rh2+ cations by mass-spectrometry based experiments and DFT-based theoretical analysis. Different reactivity has been found for these cations: Au2+ has the lowest reactivity, and it can activate methane but only produce H–Au2–CH3+ without H2 release; Rh2+ has the highest reactivity, and it can produce both carbene-type Rh2–CH2+ and carbyne-type H–Rh2–CH+ with H2 release; AuRh+ also has high reactivity to produce only AuRh–CH2+ with H2, avoiding the excessive dehydrogenation of CH4. Our theoretical results demonstrate that Rh is responsible for the high reactivity, while Au leads to selectivity, which may be caused by the unique intrinsic bonding properties of the metals.