Accelerating Pd Electrocatalysis for CO₂-to-Formate Conversion across a Wide Potential Window by Optimized Incorporation of Cu

Electrochemical reduction of carbon dioxide (CO₂) to formate is a viable way to reduce CO₂emissions and realize a carbon-neutral energy cycle. Although Pd can convert CO₂to formate with a high Faradaic efficiency at minimal overpotentials, it suffers from a limited and narrow potential window. Alloying is an important strategy for the catalyst design and tuning the electronic structures. Here, we report a series of PdCu bimetallic alloy catalysts with tunable compositions based on dendritic architectures. Optimal introduction of Cu atoms into the Pd matrix facilitates formate production and suppresses CO generation. In 0.1 M KHCO₃aqueous solution, our best candidate, Pd₈₂Cu₁₈catalyst, delivered a high formate Faradaic efficiency of 96.0% at -0.3 V versus RHE. More interestingly, the high selectivity (>90%) toward formate maintained an enlarged electrochemical potential window of 600 mV. The ensemble effect with electronic coupling between Pd and Cu upon alloying and its induced moderate surface O-containing configuration were found to enhance the formate formation and suppress CO poisoning during CO₂reduction.