Steering the Absorption Configuration of Intermediates over Pd-Based Electrocatalysts toward Efficient and Stable CO2 Reduction

Palladium (Pd) catalysts are promising for electrochemical reduction of CO2 to CO but often can be deactivated by poisoning owing to the strong affinity of *CO on Pd sites. Theoretical investigations reveal that different configurations of *CO endow specific adsorption energies, thereby dictating the final performances. Here, a regulatory strategy toward *CO absorption configurations is proposed to alleviate CO poisoning by simultaneously incorporating Cu and Zn atoms into ultrathin Pd nanosheets (NSs). As-prepared PdCuZn NSs can catalyze CO production at a wide potential window (−0.28 to −0.78 V vs RHE) and achieve a maximum FECO of 96% at −0.35 V. Impressively, it exhibits stable CO production of 100 h under ∼95% FECO with no decay. Combined results from X-ray analysis, in situ spectroscopy, and theoretical simulations suggest that the codoping strategy not only optimizes the electronic structure of Pd but also weakens the binding strengths of *CO and increases the proportion of weak-binding linear *CO absorption configuration on catalysts' surfaces. Such targeted adoption of weakly bound configurations abates the energy barrier of *CO desorption and facilitates CO production. This work confers a useful design tactic toward Pd-based electrocatalysts, codoping for steering adsorption configuration to achieve highly selective and stable CO2-to-CO conversion.