Evidence To Challenge the Universality of the Horiuti鈥揚olanyi Mechanism for Hydrogenation in Heterogeneous Catalysis: Origin and Trend of the Preference of a Non-Horiuti鈥揚olanyi Mechanism

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• 作者：Bo Yang ; Xue-Qing Gong ; Hai-Feng Wang ; Xiao-Ming Cao ; John J. Rooney ; P. Hu
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：October 9, 2013
• 年：2013
• 卷：135
• 期：40
• 页码：15244-15250
• 全文大小：495K
• 年卷期：v.135,no.40(October 9, 2013)
• ISSN：1520-5126

文摘

The Horiuti鈥揚olanyi mechanism has been considered to be universal for explaining the mechanisms of hydrogenation reactions in heterogeneous catalysis for several decades. In this work, we examine this mechanism for the hydrogenation of acrolein, the simplest 伪,尾-unsaturated aldehyde, in gold-based systems as well as some other metals using extensive first-principles calculations. It is found that a non-Horiuti鈥揚olanyi mechanism is favored in some cases. Furthermore, the physical origin and trend of this mechanism are revealed and discussed regarding the geometrical and electronic effects, which will have a significant influence on current understandings on heterogeneous catalytic hydrogenation reactions and the future catalyst design for these reactions.