Regulating Ru<sub><i>x</i></sub>Mo<sub><i>y</i></sub> Nanoalloys Anchored on Porous Nitrogen-Doped Carbon via Domain-Confined Etching Strategy for Neutral Efficient Ammonia Electrosynthesis.

Ge, Xin; Pan, Ronglan; Xie, Haibo; Hu, Shiwei; Yuan, Jili · Nano Lett · 2024

basic_science · Level V

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Abstract

Neutral electrochemical nitrate (NO<sub>3</sub><sup>-</sup>) reduction to ammonia involves sluggish and complex kinetics, so developing efficient electrocatalysts at low potential remains challenging. Here, we report a domain-confined etching strategy to construct Ru<sub><i>x</i></sub>Mo<sub><i>y</i></sub> nanoalloys on porous nitrogen-doped carbon by optimizing the Ru-to-Mo ratio, achieving efficient neutral NH<sub>3</sub> electrosynthesis. Combining <i>in situ</i> spectroscopy and theoretical simulations demonstrated a rational synergic effect between Ru and Mo in nanoalloys that reinforces *H adsorption and lowers the energy barrier of NO<sub>3</sub><sup>-</sup> hydrodeoxygenation for NH<sub>3</sub> production. The resultant Ru<sub>5</sub>Mo<sub>5</sub>-NC surpasses 92.8% for NH<sub>3</sub> selectivity at the potential range from -0.25 to -0.45 V vs RHE under neutral electrolyte, particularly achieving a high NH<sub>3</sub> selectivity of 98.3% and a corresponding yield rate of 1.3 mg h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup> at -0.4 V vs RHE. This work provides a synergic strategy that sheds light on a new avenue for developing efficient multicomponent heterogeneous catalysts.