Si-Doped Fe Catalyst for Ammonia Synthesis at Dramatically Decreased Pressures and Temperatures

The Haber–Bosch (HB) process combining nitrogen (N₂) and hydrogen (H₂) into ammonia (NH₃) gas plays an essential role in the synthesis of fertilizers for food production and many other commodities. However, HB requires enormous energy resources (2% of world energy production), and the high pressures and temperatures make NH₃ production facilities very expensive. Recent advances in improving HB catalysts have been incremental and slow. To accelerate the development of improved HB catalysts, we developed a hierarchical high-throughput catalyst screening (HHTCS) approach based on the recently developed complete reaction mechanism to identify non-transition-metal (NTM) elements from a total set of 18 candidates that can significantly improve the efficiency of the most active Fe surface, Fe-bcc(111), through surface and subsurface doping. Surprisingly, we found a very promising subsurface dopant, Si, that had not been identified or suggested previously, showing the importance of the subsurface Fe atoms in N₂ reduction reactions. Then we derived the full reaction path of the HB process for the Si doped Fe-bcc(111) from QM simulations, which we combined with kinetic Monte Carlo (kMC) simulations to predict a ∼13-fold increase in turnover frequency (TOF) under typical extreme HB conditions (200 atm reactant pressure and 500 °C) and a ∼43-fold increase in TOF under ideal HB conditions (20 atm reactant pressure and 400 °C) for the Si-doped Fe catalyst, in comparison to pure Fe catalyst. Importantly, the Si-doped Fe catalyst can achieve the same TOF of pure Fe at 200 atm/500 °C under much milder conditions, e.g. at a much decreased reactant pressure of 20 atm at 500 °C, or alternatively at temperature and reactant pressure decreased to 400 °C and 60 atm, respectively. Production plants using the new catalysts that operate under such milder conditions could be much less expensive, allowing production at local sites needing fertilizer.