基于第一性原理计算的反式-2-丁烯分子在 Pd(110)表面的吸附和脱氢反应。

First-principles calculations of adsorption and dehydrogenation of trans-2-butene molecule on Pd(110) surface.

机构信息

Hefei National Laboratory for Physical Science at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.

出版信息

J Chem Phys. 2009 Oct 21;131(15):154703. doi: 10.1063/1.3234419.

DOI:10.1063/1.3234419

PMID:20568876

Abstract

Adsorption and dehydrogenation processes of trans-2-butene molecule on the Pd(110) surface have been studied by density functional theory calculations. Different adsorption configurations of the reactant, the dehydrogenated product, and the most favorable reaction pathway have been determined. The calculated energy barrier agrees well with the value deduced from experiments. It is found that the reactant molecule must undergo a rotation before the C-H bond cleavage, and surface Pd atoms are involved in the dehydrogenation reaction through the formation of the Pd-C-H three-membered metallacycle. Our calculations have not only provided reliable interpretation for various experimental observations but also shed more light on the dynamics of the reaction processes.

摘要

采用密度泛函理论计算研究了反式-2-丁烯分子在 Pd(110)表面上的吸附和脱氢过程。确定了反应物、脱氢产物的不同吸附构型和最有利的反应途径。计算出的能量势垒与从实验中推断出的值吻合较好。结果表明，在 C-H 键断裂之前，反应物分子必须先经历旋转，并且表面 Pd 原子通过形成 Pd-C-H 三元金属环参与脱氢反应。我们的计算不仅为各种实验观察提供了可靠的解释，而且还揭示了反应过程的动力学。