First-principles study of some factors controlling the rate of ammonia decomposition on Ni and Pd surfaces

Using the plane-wave pseudopotential method within the density-functional theory with the generalized gradient approximation for exchange and correlation potential, we have calculated adsorption energies (E-ad), diffusion barrier, and the first dissociation barrier (E-1) for NH3 on Ni and Pd surfaces. While the top site is found to be preferred for NH3 adsorption on both Ni(111) and Pd(111), its calculated diffusion barrier is substantially higher for Pd(111) than for Ni(111). We also find that during the first dissociation step (NH(3)double right arrow NH2+H), NH2 moves from the top site to the nearest hollow site on Ni(111) and Pd(111) and on the stepped surfaces, Ni(211) and Pd(211), it moves from the initial top site at the step edge to the bridge site in the same atomic chain. Meanwhile H is found to occupy the hollow sites on all four surfaces. On Ni(111), E-1 is found to be 0.23 eV higher than E-ad, while at the step of Ni(211), E-1 and E-ad are almost equal, suggesting that the probability for the molecule to dissociate is much on the step of Ni(211). In the case of Pd(211), however, we find that the dissociation barrier is much higher than E-ad. These trends are in qualitative agreement with the experimental finding that ammonia decomposition rate is much lower on Pd than on Ni