Theoretical Exploration on the Role of Magnetic States to the N2 Fixation behaviors of 2D Transition Metal Tri‐borides (TMB3s).

Fixing nitrogen (N2) by electrosynthesis method has become a promising way to ammonia (NH3) production, nevertheless, developing electrocatalysts combining long‐term stable and low‐cost feathers are still a great challenge to date. Using comprehensive first‐principles calculations, we herein investigate the potential of a new class of two‐dimensional (2D) transition metal tri‐borides (TMB3s) as nitrogen reduction reaction (NRR) electrocatalysts, and explore the effect of magnetic orders on the NRR. Our results show that the TMB3s can sufficiently activate N2 and convert it to NH3. Particularly, TiB3 is identified as a high‐efficiency catalyst for NRR because of its low limiting potential (−0.24 V) and good suppression of the competitive hydrogen evolution reaction (HER). For the first time, we present that these TMB3s with various magnetic states exhibit different performances in the adsorption of N2 and NRR intermediates, and minor effect on activation of N2. Besides, VB3, CrB3, MnB3, and FeB3 monolayers possess the superior capacity to suppress surface oxidation via the self‐activating process, which reduces *O/*OH into *H2O under NRR electrochemical conditions, thus favoring the N2 electroreduction. This work paves the way for finding high‐performance NRR catalysts for transition metal borides and pioneering the research of magnetic states effects in NRR. [ABSTRACT FROM AUTHOR]