Insights of active sites separation mechanism for highly efficient electrocatalytic N₂ reduction to ammonia over glucose-induced metallic MoS₂

Substituting the Haber-Bosch process with electrocatalytic N₂ reduction reaction (NRR) is expected to be realized by optimizing the active sites to boost the sluggish N₂ adsorption and the hydrogenation process without interference by the thermodynamically favored hydrogen evolution reaction (HER). Herein, a phase engineering strategy for MoS₂ toward NRR is reported. The 1T phase are found to enhance the NRR activity with strong N₂ adsorption. Then, the active site separation can weaken the competitive adsorption between H⁺ and N₂ reactant on the Mo-edge, improving the NRR selectivity. More importantly, the HER selective basal plane can serve as an H-provider to further accelerate the hydrogenation process of NRR. The optimal MoS₂/C-0.4 possesses a high ammonia yield rate of 80.38 μg h^–1 mg^–1_cat. and Faradaic efficiency (FE) of 23.76%, outperforming almost all MoS₂-based electrocatalysts and beyond. This work sheds light on synchronizing the catalytic activity and selectivity for catalytic reactions. © 2023 Elsevier B.V.