signature=79bbe616a3c83bdce4ba49cc3bd8cb7f,Oxygen Vacancy-Assisted Coupling and Enolization of Aceta...

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.

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