Ru-Ni alloy nanosheets as tandem catalysts for electrochemical reduction of nitrate to ammonia

Developing electrocatalysts that exhibit both high activity and ammonia selectivity for nitrate reduction is a significant and demanding challenge, primarily due to the complex nature of the multiple-electron reduction process involved. An encouraging approach involves coupling highly active precious metals with transition metals to enhance catalytic performance through synergy. Here, we report a ruthenium-nickel alloy catalyst with nanosheets (Ru-Ni NSs) structure that achieves a remarkable ammonia Faradaic efficiency of approximately 95.93%, alongside a yield rate of up to 6.11 g.h(-1).cm(-2). Moreover, the prepared Ru-Ni NSs exhibit exceptional stability during continuous nitrate reduction in a flow reactor for 100 h, maintaining a Faradaic efficiency of approximately 90% and an ammonia yield of 37.4 mg.L-1.h(-1) using 0.05 M nitrate alkaline electrolyte. Mechanistic studies reveal that the catalytic process follows a two-step pathway, in which HONO serves as a migration intermediate. The presence of a partially oxidized Ru (002) surface enhances the adsorption of nitrate and facilitates the release of the migration intermediate by adjusting the strength of the electrostatic and covalent interactions between the adsorbate and the surface, respectively. On the other hand, the Ni (111) surface promotes the utilization of the migration intermediate and requires less energy for NH3 desorption. This tandem process contributes to a high catalytic activity of Ru-Ni NSs towards nitrate reduction.