Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis.

Abstract

Novel approaches to efficient ammonia synthesis at an ambient pressure are actively sought out so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis--ruthenium-loaded 12CaO·7Al2O3 electride (Ru/C12A7:e(-))--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:e(-) is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-Hn species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:e(-) surface is proposed on the basis of observed hydrogen absorption/desorption kinetics.