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乙烯在RuO₂(110)表面的吸附与相互作用。

Adsorption and interaction of ethylene on RuO2(110) surfaces.

作者信息

Paulus U A, Wang Y, Bonzel H P, Jacobi K, Ertl G

机构信息

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany.

出版信息

J Phys Chem B. 2005 Feb 17;109(6):2139-48. doi: 10.1021/jp049080+.

Abstract

Ethylene (C2H4) adsorbed on the stoichiometric and oxygen-rich RuO2(110) surfaces, exposing coordinatively unsaturated Ru-cus and O-cus atoms, is investigated by applying high-resolution electron energy-loss spectroscopy and thermal desorption spectroscopy in combination with isotope labeling experiments. On the stoichiometric RuO2(110) surface C2H4 adsorbs and desorbs molecularly. In contrast, on the oxygen-rich RuO2(110) surface ethylene adsorbs molecularly at 85 K and is completely oxidized through interaction with O-cus and O-bridge upon annealing to 500 K. The first couple of reactions are observed at 200 K taking place on Ru-cus: A change from pi- to sigma-bonding, formation of -C=O and -C-O groups, and dehydrogenation giving rise to H2O adsorbed at Ru-cus. Maximum reaction rate is reached for C2H4 chemisorbed at Ru-cus with O-cus neighbors on each side. A model for the first couple of reactions is sketched. For the final combustion, C2H4 reacts both with O-cus and O-bridge. Ethylene oxide is not detected under any circumstance.

摘要

通过结合高分辨率电子能量损失谱、热脱附谱以及同位素标记实验,对吸附在化学计量比和富氧的RuO₂(110)表面上的乙烯(C₂H₄)进行了研究,这些表面暴露了配位不饱和的Ru-cus和O-cus原子。在化学计量比的RuO₂(110)表面上,C₂H₄以分子形式吸附和解吸。相比之下,在富氧的RuO₂(110)表面上,乙烯在85 K时以分子形式吸附,在退火至500 K时通过与O-cus和O-桥相互作用而完全氧化。最初的几个反应在200 K时观察到,发生在Ru-cus上:从π键到σ键的转变、-C=O和-C-O基团的形成以及脱氢生成吸附在Ru-cus上的H₂O。当C₂H₄在Ru-cus上化学吸附且两侧都有O-cus邻居时,达到最大反应速率。勾勒了最初几个反应的模型。对于最终的燃烧,C₂H₄与O-cus和O-桥都发生反应。在任何情况下都未检测到环氧乙烷。

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