Molybdenum carbide phase effects in heterogeneous catalytic ammonia synthesis

Abstract

The design of an efficient catalyst utilizing non-precious metals is a top priority in ammonia synthesis, and Mo is found to be inferior in ammonia synthesis due to strong nitrogen adsorption. The carburization of Mo species might be an ideal strategy for optimizing nitrogen adsorption energy and ammonia synthesis activity. In this work, we prepare two molybdenum carbides with different crystal structures (α-MoC and β-Mo2C). The result shows that there is a larger number of Mo-C bonds and lower Mo/C ratio in α-MoC, leading to the strong adsorption of hydrogen and ammonia species on α-MoC. In contrast, the desorption energies of hydrogen and ammonia are lower for β-Mo2C, and the spillover and migration of hydrogen species are boosted. The facile desorption of hydrogen and ammonia species also limits the accumulation of H adatoms and ammonia on the surface of β-Mo2C, releasing of active sites available for the subsequent activation of hydrogen and nitrogen as well as ammonia synthesis reaction. As a result, the ammonia synthesis activity of β-Mo2C catalyst is 2.5-fold higher than that of α-MoC, and a small negative value of NH3 reaction order also would be obtained for β-Mo2C. This work not only reports the effect of molybdenum carbide phases on the adsorption–desorption properties of reactants and catalytic activities for ammonia synthesis, but also opens a perspective for the design and development of efficient metal based heterogeneous catalysts by tuning the adsorption and desorption properties of the reactant gases. Keywords: Molybdenum Carbide; Phase effect; Adsorption–desorption property; Mo catalyst; Ammonia synthesis