The synthesis of ammonia in the Haber-Bosch process produces millions of tons of ammonia annually needed for producing fertilisers required to feed the growing population. Although this process has been optimised extensively, it still accounts for about 2% of global energy consumption. It is, therefore, desirable to develop an efficient ammonia synthesis catalyst. Over the last decades, many attempts have been made to improve the ammonia synthesis catalyst efficiency under mild conditions. Here, we studied the effect of adding Ca and Ba to the cobalt ammonia synthesis catalyst. The combination of the different experimental results allows concluding that Ca served as an inactive additive, whereas Ba served as an electronic promoter. The Ca addition did not change the textural, structural, and chemisorptive properties of the Ca-doped Co catalyst. On the other hand, the Ba addition had a major effect on the nature of active Co sites. It contributed to the formation of new active sites for hydrogen and nitrogen adsorption and dissociation. Barium addition also contributed to the generation of new basic sites, particularly the strong ones. These unique characteristics were ascribed to the formation of Co(core)-BaO(shell) structures. It is likely that the donation of electrons from BaO to N2 via Co markedly promoted ammonia synthesis. This catalyst exhibited ammonia synthesis activity 4 times higher than that of the undoped Co catalyst and 2 times higher than that of the industrial Fe catalysts under identical conditions.
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