Oxygen and Hydroxyl Species Induce Multiple Reaction Pathways for the Partial Oxidation of Allyl Alcohol on Gold

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• 作者：Gregory M. Mullen ; Liang Zhang ; Edward J. Evans ; Jr. ; Ting Yan ; Graeme Henkelman ; C. Buddie Mullins
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：April 30, 2014
• 年：2014
• 卷：136
• 期：17
• 页码：6489-6498
• 全文大小：528K
• 年卷期：v.136,no.17(April 30, 2014)
• ISSN：1520-5126

文摘

Partial oxidation of alcohols is a topic of great interest in the field of gold catalysis. In this work, we provide evidence that the partial oxidation of allyl alcohol to its corresponding aldehyde, acrolein, over oxygen-precovered gold surfaces occurs via multiple reaction pathways. Utilizing temperature-programmed desorption (TPD) with isotopically labeled water and oxygen species, reactive molecular beam scattering, and density functional theory (DFT) calculations, we demonstrate that the reaction mechanism for allyl alcohol oxidation is influenced by the relative proportions of atomic oxygen and hydroxyl species on the gold surface. Both atomic oxygen and hydroxyl species are shown to be active for allyl alcohol oxidation, but each displays a different pathway of oxidation, as indicated by TPD measurements and DFT calculations. The hydroxyl hydrogen of allyl alcohol is readily abstracted by either oxygen adatoms or adsorbed hydroxyl species on the gold surface to generate a surface-bound allyloxide intermediate, which then undergoes 伪-dehydrogenation via interaction with an oxygen adatom or surface hydroxyl species to generate acrolein. Mediation of a second allyloxide with the hydroxyl species lowers the activation barrier for the 伪-dehydrogenation process. A third pathway exists in which two hydroxyl species recombine to generate water and an oxygen adatom, which subsequently dehydrogenates allyloxide. This work may aid in the understanding of oxidative catalysis over gold and the effect of water therein.