Redox-mediated C–C bond scission in alcohols adsorbed on CeO_{2− x} thin films

Abstract The decomposition mechanisms of ethanol and ethylene glycol on well-ordered stoichiometric CeO2(111) and partially reduced CeO2−x (111) films were investigated by means of synchrotron radiation photoelectron spectroscopy, resonant photoemission spectroscopy, and temperature programmed desorption. Both alcohols partially deprotonate upon adsorption at 150 K and subsequent annealing yielding stable ethoxy and ethylenedioxy species. The C–C bond scission in both ethoxy and ethylenedioxy species on stoichiometric CeO2(111) involves formation of acetaldehyde-like intermediates and yields CO and CO2 accompanied by desorption of acetaldehyde, H2O, and H2. This decomposition pathway leads to the formation of oxygen vacancies. In the presence of oxygen vacancies, C–O bond scission in ethoxy species yields C2H4. In contrast, C–C bond scission in ethylenedioxy species on the partially reduced CeO2−x (111) is favored with respect to C–O bond scission and yields methanol, formaldehyde, and CO accompanied by the desorption of H2O and H2. Still, scission of C–O bonds on both sides of the ethylenedioxy species yields minor amounts of accompanying C2H4 and C2H2. C–O bond scission is coupled with a partial recovery of the lattice oxygen in competition with its removal in the form of water.