Electronic Perturbation of Isolated Fe Coordination Structure for Enhanced Nitrogen Fixation

Modulation of the local electronic structure of isolated coordination structures plays a critical role in electrocatalysis yet remains a grand challenge. Herein, we have achieved electron perturbation for the isolated iron coordination structure via tuning the iron spin state from a high spin state (FeN₄) to a medium state (FeN₂B₂). The transition of spin polarization facilitates electron penetration into the antibonding π orbitals of nitrogen and effectively activates nitrogen molecules, thereby achieving an ammonia yield of 115 μg h^-1 mg^-1_cat. and a Faradaic efficiency of 24.8%. In situ spectroscopic studies and theoretical calculations indicate that boron coordinate sites, as electron acceptors, can regulate the adsorption energy of N_xH_y intermediates on the Fe center. FeN₂B₂ sites favor the NNH* intermediate formation and reduce the energy barrier of rate-determining steps, thus accounting for excellent nitrogen fixation performance. Our strategy provides an effective approach for designing efficient electrocatalysts via precise electronic perturbation.