Insights into the mechanism of acetic acid hydrogenation to ethanol on Cu(111) surface

Density functional theory (DFT) calculations were employed to theoretically explain the reaction mechanism of acetic acid hydrogenation to ethanol on Cu catalyst. The activation barriers of key elementary steps and the adsorption configurations of key intermediates involved in acetic acid hydrogenation on Cu(111) surface were investigated. The results indicated that the direct dissociation of acetic acid to acetyl (CH3COOH -> CH3CO + OH) is the rate-determined step. The activation barrier of acetic acid scission to acetyl and the adsorption energy of acetic acid are two descriptors which could determine the conversion of acetic acid. The descriptors might have effects on the ethanol selectivity including: the adsorption energy of acetaldehyde and the activation barriers for O-H bond formation of C-2-oxygenates (CH3CO + H -> CH3COH, CH3CHO + H CH3CHOH and CH3CH2O + H -> CH3CH2OH). These proposed descriptors could be used as references to design new Cu-based catalysts that have excellent catalytic performance. (C) 2017 Elsevier B.V. All rights reserved.