摘要:
The temperature-dependent adsorption and reaction ofacetaldehyde(CH3CHO) on a fully oxidized and a highly reduced thin-filmCeO2(111) surface have been investigated using a combinationof reflection–absorption infrared spectroscopy (RAIRS) andperiodic density functional theory (DFT+U) calculations. On the fullyoxidized surface, acetaldehyde adsorbs weakly through its carbonylO interacting with a lattice Ce4+ cation in the η1-O configuration. This state desorbs at 210 K without reaction.On the highly reduced surface, new vibrational signatures appear below220 K. They are identified by RAIRS and DFT as a dimer state formedfrom the coupling of the carbonyl O and the acyl C of two acetaldehydemolecules. This dimer state remains up to 400 K before decomposingto produce another distinct set of vibrational signatures, which areidentified as the enolate form of acetaldehyde (CH2CHO).Furthermore, the calculated activation barriers for the coupling ofacetaldehyde, the decomposition of the dimer state, and the recombinativedesorption of enolate and H as acetaldehyde are in good agreementwith previously reported TPD results for acetaldehyde adsorbed onreduced CeO2(111) [Chen et al. (111) surface and play a crucial role in stabilizingand activating acetaldehyde for coupling reactions.
展开