Conversion of inert N2 molecules into NH3 via electrochemical methods is an environmentally friendly alternative to replace the
traditional Haber-Bosch process. However, the development of highly efficient catalyst is still challenging. Herein, we report a
density functional theory (DFT) based high-throughput screening to investigate the potential of 23 atomic transition metals (Sc, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, W, Pt and Au) supported on phosphorene monolayer as
electrocatalyst for nitrogen reduction reaction (NRR). Our theoretical results demonstrate that V single atom anchoring on
phosphorene monolayer exhibits good thermal stability, selectivity and excellent catalytic activity with a low overpotential of 0.18 V.
Importantly, rational design principles and electronic descriptor between the intrinsic electronic properties and activation barrier have
been developed. Our work offers a new promising noble metal-free catalyst for NRR and reveals profound insights into the activity
origin to guide further design.