LAUSR

Single atomic Fe-Nx moieties have shown great performance in CO2-to-CO conversion. However, understanding the structural descriptors that determine the activity of Fe-Nx remains vague, and promising strategies to enhance their catalytic activity are still not clear. Herein, we used a high-temperature pyrolysis strategy and post-synthesis acid treatment for the direct growth of a single Fe-Nx site adjacent to graphitic nitrogen for the electrochemical CO2 reduction reaction. This strategy could significantly reduce the amount of pyridinic and pyrrolic N atoms, while graphitic N surrounding the Fe-Nx site predominantly increases. An experimental study combined with density functional theory revealed that the increase in the neighboring graphitic N decreases the number of electrons transferred between CO and the catalyst for FeN4-2N-3 and FeN4-4N-3, which results in the decrease of the adsorption strength of CO and the energy barrier for desorbing CO*. The as-synthesized Fe-Nx neighbored by graphitic nitrogen exhibited maximum faradaic efficiency of 91% at a lower overpotential of 390 mV. Due to the increase in the graphitic N, the catalysts perform efficiently for 35 h without any drop in current density.