Dramatic HER Suppression on Ag Electrodes via Molecular Films for Highly Selective CO2to CO Reduction

Arnaud Thevenon, Alonso Rosas-Hernández, Alex M. Fontani Herreros, Theodor Agapie*, Jonas C. Peters*

*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review


The carbon dioxide reduction reaction (CO2RR) in aqueous electrolytes suffers from efficiency loss due to the competitive hydrogen evolution reaction (HER). Developing efficient methods to suppress HER is a crucial step toward CO2 utilization. Herein we report the selective conversion of CO2 to CO on planar silver electrodes with Faradaic efficiencies >99% using simple pyridinium-based additives. Similar to our previous studies on copper electrodes, the additives form an organic film which alters CO2RR selectivity. We report electrochemical kinetic and other mechanistic data to shed light on the role of these organic layers in suppressing HER. These data suggest that hydrogen production is selectively inhibited by the growth of a hydrophobic organic layer on the silver surface that limits proton but not CO2 mass transport at certain applied potentials. The data also point to the involvement of a proton-transfer within the rate-determining step of the catalysis, instead of the commonly observed electron-transfer step for the case of planar Ag electrodes.

Original languageEnglish
JournalACS Catalysis
Pages (from-to)4530-4537
Number of pages8
Publication statusPublished - Apr 2021
Externally publishedYes


  • CORR
  • electrocatalysis
  • HER
  • modified electrodes
  • silver electrodes
  • solar fuels


Dive into the research topics of 'Dramatic HER Suppression on Ag Electrodes via Molecular Films for Highly Selective CO2to CO Reduction'. Together they form a unique fingerprint.

Cite this