A Comparison of the Reactivity of the Lattice Nitrogen in Tungsten Substituted Co3 Mo3 N and Ni2 Mo3 N.

ABSTRACT

The effect of the partial substitution of Mo with W in Co3 Mo3 N and Ni2 Mo3 N on ammonia synthesis activity and lattice nitrogen reactivity has been investigated. This is of interest as the coordination environment of lattice N is changed by this process. When tungsten was introduced into the metal nitrides by substitution of Mo atoms, the catalytic performance was observed to have decreased. As expected, Co3 Mo3 N was reduced to Co6 Mo6 N under a 3 1 ratio of H2 /Ar. Co3 Mo2.6 W0.4 N was also shown to lose a large percentage of lattice nitrogen under these conditions. The bulk lattice nitrogen in Ni2 Mo3 N and Ni2 Mo2.8 W0.2 N was unreactive, demonstrating that substitution with tungsten does not have a significant effect on lattice N reactivity. Computational calculations reveal that the vacancy formation energy for Ni2 Mo3 N is more endothermic than Co3 Mo3 N. Furthermore, calculations suggest that the inclusion of W does not have a substantial impact on the surface N vacancy formation energy or the N2 adsorption and activation at the vacancy site.