Lateral adsorbate interactions inhibit HCOO while promoting CO selectivity for CO2 electrocatalysis on silver

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Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO2ER). Herein, we study the role of the formate (HCOO) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton-electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface-enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O-bound bidentate species on polycrystalline Ag during CO2ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO and H2 production and a higher selectivity towards CO.

Original languageEnglish
Pages (from-to)1345-1349
JournalAngewandte Chemie - International Edition
Issue number5
Publication statusPublished - 2019


  • adsorbate-adsorbate interactions
  • DFT
  • electrocatalysis
  • in situ studies
  • Raman spectroscopy

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