Two-dimensional transition metal borides as high activity and selectivity catalysts for ammonia synthesis

Abstract

In comparison to defect/doping induced activity in materials, transition metal borides with exposed metal atoms, large specific surface area, and high active site density show advantages as durable and efficient catalysts for specific electrochemical reactions. In this work, ReB₂ for N₂ reduction reaction (NRR) for ammonia (NH₃) with a record-low limiting potential of U_L = –0.05 V and high Faraday efficiency (FE) of 100% is screened out from a new class of TMB₂. It is concluded that high pressure/temperature is favorable to N₂ adsorption and kinetic barrier minimization; the maximal turnover frequency (TOF) at 700 K and 100 bar is 1.24 × 10⁻² per s per site, which is comparable to that of the benchmark Fe₃/Al₂O₃ catalysts, achieving an extremely fast reaction rate. In addition, crystal orbital Hamilton population (COHP) of *N₂ reveals the intrinsic origin of N₂ activation by analyzing the d–2π* interactions, and integrated COHP could be a quantitative descriptor to describe the N₂ activation degree. It is evident that our results not only identify an efficient NRR electrocatalyst in particular, paving the way for sustainable NH₃ production, but also explain the chemical and physical origin of the activity, advancing the design principle for catalysts for various reactions in general.