Water-Assisted Homolytic Dissociation of Propyne on a Reduced Ceria Surface

The emergence of ceria (CeO₂ ) as an efficient catalyst for the selective hydrogenation of alkynes has attracted great attention. Intensive research effort has been devoted to understanding the underlying catalytic mechanism, in particular the H₂ -CeO₂ interaction. Herein, we show that the adsorption of propyne (C₃ H₄ ) on ceria, another key aspect in the hydrogenation of propyne to propene, strongly depends on the degree of reduction of the ceria surface and hydroxylation of the surface, as well as the presence of water. The dissociation of propyne and the formation of methylacetylide (CH₃ CC-) have been identified through the combination of infrared reflection absorption spectroscopy (IRAS) and DFT calculations. We demonstrate that propyne undergoes heterolytic dissociation on the reduced ceria surface by forming a methylacetylide ion on the oxygen vacancy site and transferring a proton to the nearby oxygen site (OH group), while a water molecule that competes with the chemisorbed methylacetylide at the vacancy site assists the homolytic dissociation pathway by rebounding the methylacetylide to the nearby oxygen site.