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This study explains a co-promoting interaction of cerium and barium additives in a cobalt catalyst used for ammonia synthesis. The results show that a synergistic effect of Ce and Ba promoters in the catalyst is associated with an emergence of a third promoter—BaCeO3—which forms in situ from its individual components during catalyst activation. The influence of perovskite-type barium cerate is substantial due to its strong basic properties, i.e. high electron-donating ability and a tendency to stabilize the Co hcp cobalt phase (more active in ammonia synthesis than the Co fcc phase). BaCeO3 diversifies the structure of adsorption sites on the cobalt surface by contributing to the exposure of facets with more favourable adsorption and binding energies with regards to rate-limiting reactions steps. It allows to a more fluent formation and transfer of species unrestricted by the hydrogen or product poisoning consequently accelerating the entire ammonia synthesis process.

Synergistic Interaction of Cerium and Barium-New Insight into the Promotion Effect in Cobalt Systems for Ammonia Synthesis