Catalytic CO oxidation by free Au2-: experiment and theory.
Catalytic CO oxidation by free Au2-: experiment and theory.
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DOI：
10.1021/ja027926m
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发表时间：
2003-08
影响因子：
15
通讯作者：
Liana D. Socaciu;J. Hagen;T. Bernhardt;L. Wöste;U. Heiz;H. Häkkinen;U. Landman
中科院分区：
文献类型：
--
作者：
Liana D. Socaciu;J. Hagen;T. Bernhardt;L. Wöste;U. Heiz;H. Häkkinen;U. Landman
变温射频离子阱质谱和第一性原理模拟揭示了O（2）存在下自由Au（2）（-）离子催化气相氧化CO的详细反应机理。在低温下观察到一个质量为Au（2）CO（3）（-）的亚稳中间体。预测了该中间体的两种替代结构，对应于digold碳酸酯或过氧甲酸酯。这两种结构的特征在于形成CO（2）的低活化势垒。这些结合的实验和理论研究提供了一个全面的理解的动力学，能量学，和原子排列沿着反应路径，从而允许制定的催化循环的氧化反应。
Temperature-dependent rf-ion trap mass spectrometry and first-principles simulations reveal the detailed reaction mechanism of the catalytic gas-phase oxidation of CO by free Au(2)(-) ions in the presence of O(2). A metastable intermediate with a mass of Au(2)CO(3)(-) was observed at low temperatures. Two alternative structures corresponding to digold carbonate or peroxyformate are predicted for this intermediate. Both structures are characterized by low activation barriers for the formation of CO(2). These combined experimental and theoretical investigations provide a comprehensive understanding of the kinetics, energetics, and atomic arrangements along the reaction path, thus allowing a formulation of the catalytic cycle for the oxidation reaction.