Suppression of Competing Reaction Channels by Pb Adatom Decoration of Catalytically Active Cu Surfaces During CO₂ Electroreduction

The direct electrochemical conversion of carbon dioxide to chemicals and fuels is of fundamental scientific and technological interest. The control of the product selectivity, expressed in terms of the Faradaic efficiency, has remained a great challenge. Herein, we describe a surface-electrochemical synthetic strategy to tune the electrochemical CO 2 reduction selectivity and yield by controlled suppression of the hydrogen evolution reaction (HER) reaction channel, resulting in increased Faradaic efficiencies for fuels and chemicals. We demonstrate that bimetallic catalysts consisting of only minute submonolayer amounts of Pb adatoms deposited on Cu surfaces exhibit and maintain unusually high selectivities for formate (HCOO – ) over a large range of overpotentials. The bimetallic adatom electrodes were prepared using underpotential electrodeposition (UPD), which is able to precisely control the adatom coverage. While as little as 0.16 ML Pb surface adatoms on a polycrystalline Cu surface boosted the observed Faradaic HCOO – product selectivity 15 times, the 0.78 ML Pb/Cu catalyst showed the most favorable ratio of HCOO – /H 2 production rate thanks to the effective suppression of the HER combined with a partial (−1.0 to −1.1 V vs RHE) enhancement of the HCOO – production. We argue that the favorable product efficiency is caused by selective adatom poisoning on the strongest binding hydrogen adsorption sites; in addition, electronic effects of Pb adatoms change the chemisorption of reactive intermediates. Our study reveals synthetic access to tailored selective bimetallic copper catalysts for the electrochemical CO 2 reduction and demonstrates the enormous effect of even minute amounts of surface adatoms on the product spectrum.