Acetic acid conversion to ketene on Cu2O(1 0 0): Reaction mechanism deduced from experimental observations and theoretical computations

Ketene, a versatile reagent in production of fine and specialty chemicals, is produced from acetic acid. We investigate the synthesis ketene acid over (3,0;1,1) surface Cu2O(1 0 0) through analysis adsorption desorption characteristics formic acids. The results allow us to establish reaction mechanism for formation. Observations x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy, temperature programmed (TPD), supported by comparison with results, suggest that reacts Cu2O deprotonation form acetate species coordinated copper sites hydroxylation nearby oxygen sites. For decomposition adsorbed formate CO2 CO while, acid, high yields are observed at >500 K. Modeling density functional theory (DFT) confirms strong interaction spontaneous dissociation into hydrogen atom species, latter forming an OH-group. In identified intermediate binds via all C O atoms Cu sites, agreement interpretations XPS. vicinity adsorbate experiences local reorganization c(2 × 2) reconstruction. total computed energy barrier formation 1.81 eV good 1.74 obtained TPD analysis. Our experimental observations mechanistic DFT studies suggests can operate as efficient catalyst green generation