Electrochemical CO 2 reduction (ECR) is one of the promising CO 2 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 CO 2 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 CO 2 -to-formate reduction.

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Although metal–N‐doped carbons are promising electrocatalysts for CO2‐to‐CO conversion due to their high conversion efficiency and current density, their commercial application is still challenging due to their narrow potential/current range. In general, a wide potential/current electrocatalyst is in high demand for industrial CO2 electrocatalysis. Controllable strategy to tune N configurations toward pyridinic‐enriched metal–Nx active sites is attractive. The synergetic effect of the ability of pyridinic N to capture Lewis acidic CO2 and the characteristics of Ni–N active sites to inhibit the hydrogen evolution reaction (HER) can achieve a wide potential window, which has high practical value. Herein, the well‐chosen precursors resulting in a pyridinic‐enriched Ni–Nx site can selectively catalyze CO2 toward CO generation in aqueous media with a high Faradaic efficiency (FE) of 100% with an overpotential of 680 mV. Continuous CO FE > 90% was recorded under a wide range of potentials without decay. Motivated by its practical characteristics in CO2 electrocatalysts, a Zn–CO2 battery is assembled achieving a CO2–CO conversion efficiency of more than 90% in a wide discharge current window. Therefore, the results highlight that pyridinic‐enriched Ni–Nx holds great promise as simultaneous CO‐selective electrocatalyst by suitably tuning M–N configurations as new perspective strategy.