The Selective Species in Ethylene Epoxidation on Silver

Travis E. Jones, Regina Wyrwich, Sebastian Böcklein, Emilia A. Carbonio, Mark T. Greiner, Alexander Yu Klyushin, Wolfgang Moritz, Andrea Locatelli, Tefvik O. Menteş, Miguel A. Niño, Axel Knop-Gericke, Robert Schlögl, Sebastian Günther, Joost Wintterlin, Simone Piccinin

Research output: Contribution to journalArticlepeer-review

61 Scopus citations


Silver's unique ability to selectively oxidize ethylene to ethylene oxide under an oxygen atmosphere has long been known. Today it is the foundation of ethylene oxide manufacturing. Yet, the mechanism of selective epoxide production is unknown. Here we use a combination of ultrahigh vacuum and in situ experimental methods along with theory to show that the only species that has been shown to produce ethylene oxide, the so-called electrophilic oxygen appearing at 530.2 eV in the O 1s spectrum, is the oxygen in adsorbed SO4. This adsorbate is part of a 2D Ag/SO4 phase, where the nonstoichiometric surface variant, with a formally S(V+) species, facilitates selective transfer of an oxygen atom to ethylene. Our results demonstrate the significant and surprising impact of a trace impurity on a well-studied heterogeneously catalyzed reaction.

Original languageEnglish
Pages (from-to)3844-3852
Number of pages9
JournalACS Catalysis
Issue number5
StatePublished - 4 May 2018


  • XPS
  • electrophilic oxygen
  • ethylene epoxidation
  • partial oxidation
  • silver


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