Computational screening of transition metal anchored C9N10 as the highly active and selective electrocatalysts for NH3 synthesis

Electrochemical nitrogen reduction reaction (NRR) is a very prospective approach for generating green and sustainable NH3 under mild conditions. However, the development of NRR electrocatalysts with high performance remains a huge hurdle in the field of energy conversion today. Herein, by means of first-principles calculations, we employed a hierarchical screening strategy of structural stability, catalytic activity, and selectivity to systematically investigate the potentials of a series of transition metal atoms anchored on g-C9N10 (TM@C9N10) as the electrocatalysts for NRR. Particularly, we proposed the multiple-level descriptors (φ and ICOHP), realizing the preliminary prescreening of numerous candidates. The results reveal that V@C9N10 and W@C9N10 stand out from all candidates with the significantly low limiting potentials of −0.17 V and −0.26 V, respectively. Meanwhile, they can efficiently suppress the competing hydrogen evolution reaction. Such the outstanding activity can be attributed to the donation-feedback process between the d-electrons of V and W atoms and the anti-orbitals of *N2, as well as the efficient charge transfer in hydrogenation steps. Our work not only broadens the theoretical foundation for the rational design of highly efficient SACs, but also provides an attempt to develop the NRR electrocatalysts with high activity and selectivity.