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

Jian Qiang Zhong, Zhong Kang Han, Kristin Werner, Xiao Yan Li, Yi Gao, Shamil Shaikhutdinov, Hans Joachim Freund

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)


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 (C3H4) 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 (CH3CC-) 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.

Original languageEnglish
Pages (from-to)6150-6154
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number15
Publication statusPublished - 6 Apr 2020


  • alkyne hydrogenation
  • ceria
  • dissociation
  • oxygen vacancies
  • propyne adsorption


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