Creating Highly Active Iron Sites in Electrochemical N₂ Reduction by Fabricating Strongly-Coupled Interfaces

Electrochemical N_c reduction has been regarded as one of the most promising approaches to producing ammonia under mild conditions, but there are remaining pressing challenges in improving the reaction rate and efficiency. Herein, an unconventional galvanic replacement reaction is reported to fabricate a unique hierarchical structure composed of Fe₃ O₄ -CeO₂ bimetallic nanotubes covered by Fe₂ O₃ ultrathin nanosheets. Control experiments reveal that CeO₂ species play the essential role of stabilizer for Fe²⁺ cations. Compared with bare CeO₂ and Fe₂ O₃ nanotubes, the as-obtained Fe₂ O₃ /Fe₃ O₄ -CeO₂ possesses a remarkably enhanced NH₃ yield rate (30.9 µg h^-1 mg_cat ^-1 ) and Faradaic efficiency (26.3%). The enhancement can be attributed to the hierarchical feature that makes electrodes more easily to contact with electrolytes. More importantly, as verified by density functional theory calculations, the generation of Fe₂ O₃ -Fe₃ O₄ heterogeneous junctions can efficiently optimize the reaction pathways, and the energy barrier of the potential determining step (the *N₂ hydrogenates into *N*NH) is significantly decreased.