A density functional theory study of stepwise addition reactions in ammonia synthesis on Ru(0 0 0 1)

To shed light on stepwise addition reactions in ammonia synthesis, density functional theory calculations are carried out to investigate NHx (x=1–3) formation on Ru(0 0 0 1). The reactions on a flat surface are first examined. Transition states and reaction barriers are determined. It is found that the reaction barriers for these stepwise addition reactions are rather high. For example, the barrier for NH hydrogenation is calculated to be 1.28 eV, which is comparable with that of N2 dissociation. One of the stepwise addition reactions, NH+H→NH2, on a stepped surface is also considered. Interestingly, the reaction barrier is found to be significantly lower than that on the flat surface, but is considerably higher than that of N2 dissociation on the same stepped surface. In addition, the coverage effect on the reaction energetics is also addressed.