Regulating Spin Polarization via Axial Nitrogen Traction at Fe-N5Sites Enhanced Electrocatalytic CO2Reduction for Zn-CO2 Batteries.

Abstract

Single Fe sites have been explored as promising catalysts for the CO2reduction reaction to value-added CO. Herein, we introduce a novel molten salt synthesis strategy for developing axial nitrogen-coordinated Fe-N5sites 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 FeN5, supported on defect-richin nitrogen-doped carbon(FeN5@DNC), exhibits superior performance in CO2RR, 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 FeN5@DNC catalyst is assembled as a reversible Zn-CO2battery 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.