Computational screening of MBene monolayers with high electrocatalytic activity for the nitrogen reduction reaction

As an emerging family of two-dimensional (2D) materials, transition metal borides (MBenes) have attracted increasing interest due to their potential applications in electrochemistry, especially electrocatalysis. In this work, we addressed six MB (M = Sc, Ti, V, Cr, Mo and W) monolayers as catalysts to explore their electrocatalytic activity for the nitrogen reduction reaction (NRR) using first-principles calculations. Our results demonstrated that N₂ molecules could be strongly adsorbed on these MB monolayers to provoke the NRR process. Furthermore, we examined five possible catalytic reaction pathways of the NRR, i.e., the alternating, distal, and three mixed pathways, on the MB monolayers with N₂ adsorption (both side-on and end-on) configurations, and screened out three highly efficient NRR catalysts: VB, CrB, and MoB monolayers with the onset potential of -0.396, -0.277, and -0.403 V, respectively. By comparison of the limiting potentials, the most effective reaction pathways of the NRR were ascertained to be the alternating pathway on the VB monolayer with the end-on configuration and the mixed I pathway on the CrB monolayer with the end-on configuration and on the MoB monolayer with the side-on configuration. Our work sheds light on the electrocatalytic mechanisms of the NRR on 2D MBenes, and provides a theoretical foundation for developing highly efficient MBene electrocatalysts for the NRR.