Stepwise dehydrogenation of ammonia on Fcc-Co surfaces: A DFT study

Abstract

The stepwise dehydrogenation of ammonia on clean and O-covered Co surfaces have been studied by performing density functional theory (DFT) calculations. It is found that the interaction of species NHx (x=0–3) with the Co surfaces become stronger with its further dehydrogenation, and oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation. Specifically, pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. In contrast, the dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces, due to the high energy barriers. And present results demonstrate that the species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom.