How Dynamics Changes Ammonia Cracking on Iron Surfaces

Being rich in hydrogen and easy to transport, ammonia is a promising hydrogen carrier. However, a microscopic characterization of the ammonia cracking reaction is still lacking, hindered by extreme operando conditions. Leveraging state-of-the-art molecular dynamics, machine learning potentials, and enhanced sampling methods, we offer an atomistic view of the adsorption, diffusion, and dehydrogenation processes of a single NHx (x = 1, 3) molecule on two representative surfaces at the operando temperature of 700 K. We elucidate the effects of the dynamics on all the steps of decomposition. On the stable (110) surface, we found that the reaction intermediate diffusions are favored over dehydrogenation, with non-negligible effects on the reactivity for one intermediate. The role is even more dramatic on the (111) surface, where the mobility of Fe surface atoms introduces unexplored adsorption sites and significantly alters the dehydrogenation barriers. In both cases, a detailed analysis of reactive events shows that there is never a single transition state, but it is always an ensemble. Notwithstanding, a unified mechanism can be identified by following the charge transfer along the different reaction pathways.