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

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/FeP₄) heterostructure is prepared mechanochemically with high transient pressure by the solid-phase ball milling approach. The BP/FeP₄ heterostructure delivers excellent catalytic performance in the nitrogen reduction reaction (NRR) as exemplified by an NH₃ yield of 77.6 µg h⁻¹ (Formula presented.) 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 N₂ 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.