Fluorine-Stabilized Defective Black Phosphorene as a Lithium-Like Catalyst for Boosting Nitrogen Electroreduction to Ammonia.

Electrocatalytic N 2 reduction reaction (NRR) is recognized as a zero-carbon emission method for NH 3 synthesis. However, to date, this technology still suffers from low yield and low selectivity associated with the catalyst. Herein, inspired by the activation of N 2 by lithium metal, a highly reactive defective black phosphorene (D-BP ene ) is proposed as a lithium-like catalyst for boosting electrochemical N 2 activation. Correspondingly, we also report a strategy for producing environmentally stable D-BP ene by simultaneously constructing defects and fluorination protection based on topochemical reactions. Reliable performance evaluations show that the fluorine-stabilized D-BP ene can induce a high NH 3 yield rate of ≈70 μg h -1  mg cat. -1 and a high Faradaic efficiency of ≈26 % at -0.5 V vs. RHE in an aqueous electrolyte. This work not only exemplifies the first stable preparation and practical application of D-BP ene , but also brings a new design idea for NRR catalysts.