Atomic Zn‐Doping Induced Sabatier Optimum in NiZn0.03 Catalyst for CO2 Electroreduction at Industrial‐Level Current Densities

The Sabatier principle defines the essential criteria for an ideal catalyst in heterogeneous catalysis, while reaching the Sabatier optimum is still challenging in catalyst design. Herein, an elegant strategy is described to reach the Sabatier optimum of Ni electrocatalyst in CO2 reduction reaction (CO2RR) by atomically Zn doping. The incorporation of 3% Zn single atom into Ni lattice leads to the moderate degrade of d‐band center via Ni–Zn electronic coupling, which balances the bonding strengths of *COOH and *CO, resulting in a relative low energy barrier for CO2 activation while not being substantially poisoned by CO. Consequently, NiZn0.03/C exhibits unique catalytic activity (jCO >100 mA cm−2 at −0.6 V), wide potential range for selective CO production (FECO >90% from −0.65 to −1.15 V), and outstanding long‐term stability (FECO >90% during 85 h electrolysis at −0.85 V). The results provide valuable insights for the rational fabrication of superior non‐noble bimetallic electrocatalysts in CO2 electroreduction.