Thermodynamic Constraints in Using AuM (M = Fe, Co, Ni, and Mo) Alloys as N₂ Dissociation Catalysts: Functionalizing a Plasmon-Active Metal

The Haber-Bosch process for NH₃ synthesis is arguably one of the greatest inventions of the 20th century, with a massive footprint in agriculture and, historically, warfare. Current catalysts for this reaction use Fe for N₂ activation, conducted at high temperatures and pressures to improve conversion rate and efficiency. A recent finding shows that plasmonic metal nanoparticles can either generate highly reactive electrons and holes or induce resonant surface excitations through plasmonic decay, which catalyze dissociation and redox reactions under mild conditions. It is therefore appealing to consider AuM (M = Fe, Co, Ni, and Mo) alloys to combine the strongly plasmonic nature of Au and the catalytic nature of M metals toward N₂ dissociation, which together might facilitate ammonia production. To this end, through density functional theory, we (i) explore the feasibility of forming these surface alloys, (ii) find a pathway that may stabilize/deactivate surface M substituents during fabrication, and (iii) define a complementary route to reactivate them under operational conditions. Finally, we evaluate their reactivity toward N₂, as well as their ability to support a pathway for N₂ dissociation with a low thermodynamic barrier. We find that AuFe possesses similar appealing qualities, including relative stability with respect to phase separation, reversibility of Fe oxidation and reduction, and reactivity toward N₂. While AuMo achieves the best affinity toward N₂, its strong propensity toward oxidation could greatly limit its use.