Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111)

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• 作者：Selma Şenozan ; Hande Ustunel ; Mustafa Karatok ; Evgeny I. Vovk…
• 关键词：Density functional theory ; van der Waals ; Adsorption energy ; Partial oxidation ; Alcohols ; Heterogeneous catalyst
• 刊名：Topics in Catalysis
• 出版年：2016
• 出版时间：September 2016
• 年：2016
• 卷：59
• 期：15-16
• 页码：1383-1393
• 全文大小：2,011 KB
• 刊物主题：Catalysis; Physical Chemistry; Pharmacy; Industrial Chemistry/Chemical Engineering; Characterization and Evaluation of Materials;
• 出版者：Springer US
• ISSN：1572-9028
• 卷排序：59

文摘

Gold-based heterogeneous catalysts have attracted significant attention due to their selective partial oxidation capabilities, providing promising alternatives for the traditional industrial homogeneous catalysts. In the current study, the energetics of adsorption/desorption of alcohols (CH₃OH/methanol, CH₃CH₂OH/ethanol, CH₃CH₂CH₂OH/n-propanol) and esters (HCOOCH₃/methyl formate, CH₃COOCH₃/methyl acetate, and CH₃COOCH₂CH₃/ethyl acetate) on a planar Au(111) surface was investigated in conjunction with oxidative coupling reactions by means of temperature programmed desorption (TPD) and dispersion-corrected density functional theory (DFT) calculations. The results reveal a complex interplay between inter-molecular and surface-molecule interactions, both mediated by weak van der Waals forces, which dictates their relative stability on the gold surface. Both experimental and theoretical adsorption/desorption energies of the investigated esters are lower than those of the alcohols from which they originate through oxidative coupling reactions. This result can be interpreted as an important indication in favor of the selectivity of Au surfaces in alcohol oxidative coupling/partial oxidation reactions, allowing facile removal of partial oxidation products immediately after their generation preventing their complete oxidation to higher oxygenates.