Tackling the Activity Trend of Metal‐Loaded Metal Nitride Catalysts for NH3 Synthesis by a First‐Principles Microkinetic Study

Abstract Ammonia (NH 3 ) is one of the most widely produced chemicals globally, primarily synthesized through the Haber‐Bosch process, which requires high temperatures and pressures. Dual‐site catalysts can activate N 2 and H 2 at spatially separated sites, enabling efficient NH 3 synthesis under milder conditions. Despite the rapid experimental progress of the dual‐site catalysts (e.g., Ni‐LaN), the feasibility and design of dual‐site catalysts are challenged recently. Herein, the different metal‐loaded metal nitride catalyst models are employed, and their activity map for NH 3 synthesis is explored by the first‐principles microkinetic simulation. The optimum active region of this type of dual‐site catalyst is identified in terms of the formation energy ( E v ) of nitrogen vacancy (N vac ) on metal nitride and the adsorption energy ( E H ) of hydrogen atom on metal cluster, with E v and E H ideally located around ≈1.50 and ≈−0.30 eV, respectively. This offers a framework for designing effective metal‐loaded metal nitride catalysts for NH 3 synthesis. Importantly, this trend aligns with and rationalizes the current experimental observations of metal‐loaded metal nitride reported for NH 3 synthesis. This theoretical work provides significant insights into NH 3 synthesis on dual‐site mechanism, and provides a rational direction for designing metal‐loaded metal nitride catalysts.