How palladium inhibits CO poisoning during electrocatalytic formic acid oxidation and carbon dioxide reduction

Development of reversible and stable catalysts for the electrochemical reduction of CO₂ is of great interest. Here, we elucidate the atomistic details of how a palladium electrocatalyst inhibits CO poisoning during both formic acid oxidation to carbon dioxide and carbon dioxide reduction to formic acid. We compare results obtained with a platinum single-crystal electrode modified with and without a single monolayer of palladium. We combine (high-scan-rate) cyclic voltammetry with density functional theory to explain the absence of CO poisoning on the palladium-modified electrode. We show how the high formate coverage on the palladium-modified electrode protects the surface from poisoning during formic acid oxidation, and how the adsorption of CO precursor dictates the delayed poisoning during CO₂ reduction. The nature of the hydrogen adsorbed on the palladium-modified electrode is considerably different from platinum, supporting a model to explain the reversibility of this reaction. Our results help in designing catalysts for which CO poisoning needs to be avoided.