Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

The electrochemical N 2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH 3 . Nevertheless, developing high‐efficiency catalysts to simultaneously realize both high activity and selectivity for the development of a sustainable NRR is very critical but extremely challenging. Here, a unique plasma‐assisted strategy is developed to synthesize iridium diphosphide nanocrystals with abundant surface step atoms anchored in P,N‐codoped porous carbon nanofilms (IrP 2 @PNPC‐NF), where the edges of the IrP 2 nanocrystals are extremely irregular, and the ultrathin PNPC‐NF possesses a honeycomb‐like macroporous structure. These characteristics ensure that IrP 2 @PNPC‐NF delivers superior NRR performance with an NH 3 yield rate of 94.0 µg h −1 mg −1 cat. and a faradaic efficiency (FE) of 17.8%. Density functional theory calculations reveal that the unique NRR performance originates from the low‐coordinate step atoms on the edges of IrP 2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH 3 formation. More importantly, such a plasma‐assisted strategy is general and can be extended to the synthesis of other high‐melting‐point noble‐metal phosphides (OsP 2 @PNPC‐NF, Re 3 P 4 @PNPC‐NF, etc.) with abundant step atoms at lower temperatures.