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

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2016-09-01
Senozan, Selma
Toffoli, Hande
Karatok, Mustafa
Vovk, Evgeny I.
Shah, Asad A.
ÖZENSOY, EMRAH
Toffoli, Daniele
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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.
Density functional theory, Van der Waals, Adsorption energy, Partial oxidation, Alcohols, Heterogeneous catalyst
https://hdl.handle.net/11511/38196
TOPICS IN CATALYSIS
Department of Physics, Article

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Citation Formats
S. Senozan et al., “Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111),” TOPICS IN CATALYSIS, pp. 1383–1393, 2016, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/38196.
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