ABSTRACT The electrochemical nitrogen reduction reaction (NRR) offers a sustainable transformation of nitrogen (N 2 ) into highly valuable ammonia. However, achieving both a high ammonia yield and an Faradaic efficiency (FE) higher than 40% at practical current density remains challenging, particularly with bulk metal catalysts. Herein, we propose a shell‐protection strategy to successfully prepare phase‐pure iron powder from Fe‐based metal‐organic frameworks. Notably, the resulting iron powder