Regulating Spin Polarization via Axial Nitrogen Traction at Fe‐N5 Sites Enhanced Electrocatalytic CO2 Reduction for Zn‐CO2 Batteries

Abstract Single Fe sites have been explored as promising catalysts for the CO 2 reduction reaction to value‐added CO. Herein, we introduce a novel molten salt synthesis strategy for developing axial nitrogen‐coordinated Fe‐N 5 sites on ultrathin defect‐rich carbon nanosheets, aiming to modulate the reaction pathway precisely. This distinctive architecture weakens the spin polarization at the Fe sites, promoting a dynamic equilibrium of activated intermediates and facilitating the balance between *COOH formation and *CO desorption at the active Fe site. Notably, the synthesized FeN 5 , supported on defect‐rich in nitrogen‐doped carbon (FeN 5 @DNC), exhibits superior performance in CO 2 RR, achieving a Faraday efficiency of 99 % for CO production (−0.4 V vs. RHE) in an H‐cell, and maintaining a Faraday efficiency of 98 % at a current density of 270 mA cm −2 (−1.0 V vs. RHE) in the flow cell. Furthermore, the FeN 5 @DNC catalyst is assembled as a reversible Zn−CO 2 battery with a cycle durability of 24 hours. In situ IR spectroscopy and density functional theory (DFT) calculations reveal that the axial N coordination traction induces a transformation in the crystal field and local symmetry, therefore weakening the spin polarization of the central Fe atom and lowering the energy barrier for *CO desorption.