LAUSR

The Haber-Bosch (HB) process combining nitrogen (N2) and hydrogen (H2) into ammonia (NH3) gases 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 nor 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 turn-over 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, compared 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 50 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.