Abstract: Conversion of dinitrogen (N2) molecules into ammonia through electrochemical methods is a promising alternative to the traditional Haber-Bosch process. However, searching for an eligible electrocatalyst with high stability, low-onset potential, and superior selectivity is still one of the most challenging and attractive topics for the electrochemical N2 reduction reaction (NRR). Here, by means of first-principles calculations and the conductor-like screening model, four comprehensive criteria were proposed to screen out eligible NRR electrocatalysts from 29 atomic transition metals embedded on the defective boron phosphide (BP) monolayer with B-monovacancy (M/BP single-atom catalysts, SAC, M = Sc-Zn, Y-Cd, and Hf-Hg). Consequently, the Nb/BP and W/BP SACs are identified as the promising candidates, on which the N2 molecule can only be activated through the enzymatic pathway with the onset potentials of -0.25 and -0.19 V, and selectivities of 90.5 and 100%, respectively. It is worth noting that the W/BP SAC has the lowest overpotential among the 29 systems investigated. The electronic properties were also calculated in detail to analyze the activity origin. Importantly, the Nb/BP and W/BP SACs possess high thermal stabilities due to that their structures can be retained very well up to 1000 and 700 K, respectively. This work not only provides an efficient and reliable method to screen eligible NRR electrocatalysts but also paves a new way for advancing sustainable ammonia synthesis.
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