Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets

Constructing efficient catalysts for the N-2 reduction reaction (NRR) is a major challenge for artificial nitrogen fixation under ambient conditions. Herein, inspired by the principle of like dissolves like, it is demonstrated that a member of the nitrogen family, well-exfoliated few-layer black phosphorus nanosheets (FL-BP NSs), can be used as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve a high ammonia yield of 31.37 mu gh(-1) mg(cat.)(-1) under ambient conditions. Density functional theory calculations reveal that the active orbital and electrons of zigzag and diff-zigzag type edges of FL-BP NSs enable selective electrocatalysis of N-2 to NH3 via an alternating hydrogenation pathway. This work proves the feasibility of using a nonmetallic simple substance as a nitrogen-fixing catalyst and thus opening a new avenue towards the development of more efficient metal-free catalysts.