Regulating the Electronic Configuration of Supported Iron Nanoparticles for Electrochemical Catalytic Nitrogen Fixation

Electrocatalytic nitrogen reduction reaction (eNRR) is a sustainable alternative to the traditional Haber–Bosch process due its eco-friendly nature and capability of utilizing renewable energy. However, low Faradic efficiency (FE), caused by excessive adsorption protons, has been regarded as main challenge, which leads ammonia yield well. Herein, carbon-supported iron electrocatalyst reported, fabricated low-temperature (300 °C) potassium vapor FeF3-intercalated graphite fluoride, for efficient electrochemical reduction. The strategy enables unique formation exposed Fe nanoparticles uniformly anchored on graphene in situ doped with fluorine heteroatoms. These specific features can alter electronic configuration nanoparticles, leading strong surface polarization that boosts absorption eNRR, resulting high FE (41.6%) rate (53.3 ?g h-1 mg-1) simultaneously. First-principle calculation attributes this enhanced eNRR more empty orbitals carried atoms through electron transfer F dopant substrate. As versatile synthesizing various ultrafine highly dispersed metal carbon support, work might shed light rational designing essential electrocatalysts effective structure manipulation.