Controllable Construction of a Mo 2 C/MoO 2 Interface with an Ideal Mo 2 C/MoO 2 Ratio for Efficient Electrocatalytic Nitrogen Reduction to Ammonia.

Electrocatalytic nitrogen reduction reaction (NRR) is considered to be a viable contender for the production of NH 3 . However, due to the sluggish adsorption and activation of the electrocatalyst toward inert N 2 molecules, there is an urgent need for developing effective catalysts to facilitate the reaction. Inspired by natural nitrogenase, in which Mo atoms are the active centers, Mo-based electrocatalysts have received considerable attention, but further exploration is still necessary. Interface-engineered electrocatalysts can effectively optimize the absorption and activation of the catalytic active center for N 2 and thus improve the electrocatalytic activity of NRR. However, the lack of studies for controllably constructing an optimal ratio of two phases at the interface hinders the development of NRR electrocatalysts. Herein, a series of Mo 2 C/MoO 2 interface-engineered electrocatalysts with various Mo 2 C/MoO 2 ratios were constructed by controlling the Y dosages. The controlled experimental results verified that the catalytic activity of NRR, the dosage of Y, and the ratio of Mo 2 C/MoO 2 were strongly correlated. Density functional theory calculations show that the C-Mo-O coordination at the Mo 2 C/MoO 2 interface can optimize the reaction path and reduce the energy barrier of the reaction intermediates, thereby enhancing the reaction kinetics of NRR.