High-throughput screening of single-atom catalysts confined in monolayer black phosphorus for efficient nitrogen reduction reaction

The discovery of metal-nitrogen centers as the active sites for electrolysis has aroused significant interest in utilizing single-atom catalysts for nitrogen reduction reaction (NRR). Properly designed nanostructured catalysts that strongly interact with nitrogen molecules (N-2) can promote adsorption and activation, thereby resulting in efficient catalysts with high stability, activity, and selectivity. In this study, using density functional theory calculations, we selected monolayer black phosphorus (BP) as the substrate and screened a series of single-atom transition metals confined in tri-coordinated and tetra-coordinated active centers (without and with N dopants) to electro-catalyze NRR. As a result, we have identified two promising candidates (Hf-1-N1P2-1 and Tc-1-N-4), which exhibit not only low overpotentials of 0.56 and 0.49 V but also high thermodynamic and electrochemical stability, as well as good selectivity towards NRR over the competing hydrogen evolution reaction. We also demonstrate the ability of Hf-1-N1P2-1 and Tc-1-N-4 to activate and hydrogenate N-2 by donating electrons and regulating charge transfer. This study not only predicts new BP-based promising catalysts but also provides guidance for the rational design of high-performance NRR electrocatalysts under ambient conditions.