Fabricating Black‐Phosphorus/Iron‐Tetraphosphide Heterostructure via a Solid‐Phase Solution‐Precipitation Method for High‐Performance Nitrogen Reduction

Abstract Although constructing heterostructures is considered as one of the most successful strategies to improve the activity of a catalyst, the heterostructures usually suffer from the cumbersome preparation treatments and low‐yield. Inspired by a solid‐phase solution‐precipitation (SPSP) process, an approach for interface intensive heterostructures with high yield is developed. Herein, a black‐phosphorus/iron‐tetraphosphide (BP/FeP 4 ) heterostructure is prepared mechanochemically with high transient pressure by the solid‐phase ball milling approach. The BP/FeP 4 heterostructure delivers excellent catalytic performance in the nitrogen reduction reaction (NRR) as exemplified by an NH 3 yield of 77.6 µg h −1 and Faradic efficiency of 62.9% (−0.2 V), which are superior to that of most NRR catalysts recently reported. Experimental investigation and density‐functional theory calculation indicate the importance of excess phosphorus in the heterostructures on the NRR activity, which assists the Fe atom to activate N 2 via adsorbing the H atom. The results demonstrate the great potential of this new type of heterostructures prepared by the SPSP approach. Benefiting from the simple preparation process and low cost, the heterostructures offer a new insight into the development of highly efficient catalysts.