Dramatic HER Suppression on Ag Electrodes via Molecular Films for Highly Selective CO₂ to CO Reduction

Abstract

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.