Optimizing particle morphology: Atomic iron–nitrogen centers with graphitic‐N for highly efficient CO₂ electroreduction

Transition metal‐coordinated nitrogen sites on carbon catalysts (M‐N‐C) hold potential for CO 2 electroreduction (CO 2 ER), but optimal morphology and active sites are unclear. We introduce a novel approach, developing zeolitic imidazolate framework‐8 (ZIF‐8)‐derived carbon catalysts with Fe‐N and graphitic‐N sites (Fe 2 ‐NC) via molecular confinement and thermal activation. Fine‐tuning ZIF‐8 size and activation temperature yielded 44.98% active N sites. The 300 nm Fe2‐NC catalyst displayed outstanding CO 2 ‐to‐CO conversion, with a 170 mV overpotential and 94.3% Faradaic efficiency at −0.5 V, outperforming state‐of‐the‐art materials. Enhanced CO 2 ER kinetics and conductivity contributed to this superiority. Results highlight the correlation between maximum CO Faradaic efficiency and cumulative Fe‐N/graphitic‐N sites, dependent on size and activation. The 300 nm Fe 2 ‐NC in a gas diffusion electrode‐loaded flow cell achieved a 15.3‐fold CO partial current density increase. In a Zn‐CO 2 battery, the 300 nm Fe 2 ‐NC demonstrated a peak power density of 0.618 mW cm −2 , showcasing energy storage potential.