LAUSR

Abstract Electrocatalytic ammonia synthesis provides an energy-efficient alternative to the Haber−Bosch process. The aim is to find promising electrocatalysts which are able to change the reaction pathway and reduce the overpotential. Here, based on density functional theory, a comprehensive mechanism study of the N2 activation and NH3 synthesis on the Mo2TiC2 MXenes is presented. For catalytic reaction mechanism, nineteen different possible pathways are screened for the lowest overpotential, where the corresponding potential-determining step are compared by Gibbs free energy calculation. The result reveals Mo2TiC2 MXenes exhibit both valid N2-philicity and high catalytic activity for electrocatalytic ammonia synthesis through a dissociation mechanism with a low overpotential of 0.26 V. Further, the competing reaction of H2 evolution is simultaneously suppressed which shows a relatively high potentials of 0.74 V. This study shows a brand new material for catalyzing NH3 synthesis under ambient conditions and provides the theory background to reduce the overpotential by changing the reaction pathway.