Asymmetric Oxo‐Bridged ZnPb Bimetallic Electrocatalysis Boosting CO2‐to‐HCOOH Reduction

Electrochemical CO₂ reduction (ECR) is one of the promising CO₂ recycling technologies sustaining the natural carbon cycle and offering more sustainable higher-energy chemicals. Zn- and Pb-based catalysts have improved formate selectivity, but they suffer from relatively low current activities considering the competitive CO selectivity on Zn. Here, lead-doped zinc (Zn(Pb)) electrocatalyst is optimized to efficiently reduce CO₂ to formate, while CO evolution selectivity is largely controlled. Selective formate is detected with Faradaic efficiency (FE_HCOOH ) of ≈95% at an outstanding partial current density of 47 mA cm^-2 in a conventional H-Cell. Zn(Pb) is further investigated in an electrolyte-fed device achieving a superior conversion rate of ≈100 mA cm^-2 representing a step closer to practical electrocatalysis. The in situ analysis demonstrates that the Pb incorporation plays a crucial role in CO suppression stem from the generation of the Pb-O-C-O-Zn structure rather than the CO-boosted Pb-O-C-Zn. Density functional theory (DFT) calculations reveal that the alloying effect tunes the adsorption energetics and consequently modifies the electronic structure of the system for an optimized asymmetric oxo-bridged intermediate. The alloying effect between Zn and Pb controls CO selectivity and achieves a superior activity for a selective CO₂ -to-formate reduction.