No Time for Nitrides: How Cobalt Alloying Promotes Iron Catalysts for Ammonia Decomposition

Abstract

The increasing demand for hydrogen production has driven interest in ammonia decomposition. Iron-based catalysts, widely used for ammonia synthesis, exhibit suboptimal performance in the reverse process due to their tendency to form iron nitrides. Recent experiments have shown that alloying iron with cobalt enhances the catalytic activity (Chen et al., Nat. Commun. 15, 871, 2024), yet the microscopic origin of this promotional effect is not fully understood. To address this, we leverage recent developments in machine learning-based molecular dynamics simulations to investigate the key reactions of the catalytic cycle, fully accounting for dynamical lateral interactions on the catalyst surface. Our simulations reveal that cobalt alloying provides a dual promotional effect: it slightly lowers the free energy barrier for nitrogen recombination, which is the rate-determining step for ammonia decomposition on iron, while significantly suppressing nitrogen migration into the bulk, thereby preventing nitride formation. These insights are supported by complementary transient decomposition experiments and desorption measurements, which confirm the enhanced activity and resistance to nitridation in FeCo alloys compared to monometallic iron catalysts. Furthermore, long-term stability tests demonstrate that the FeCo catalyst sustains high ammonia conversion over extended time scales. By capturing the complex interplay of competing dynamical processes at the atomic scale, our results highlight the importance of going beyond static structure–property relationships to gain mechanistic insights that can guide the rational design of more robust and efficient catalysts.