Coupling Au with BO_x matrix induced by Closo-boron cluster for electrochemical synthesis of ammonia

Au is considered as one of the most promising catalysts for nitrogen reduction reaction (NRR), however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges. Herein, we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics. An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles (2–6 nm in diameter) loaded on BO_x substrates (Au–BO_x), in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles. The electrochemical results show that Au–BO_x possesses excellent NRR activity (NH₃ yield of 48.52 μg h⁻¹ mg_cat.⁻¹, Faraday efficiency of 56.18%), and exhibits high stability and reproducibility throughout the electrocatalytic NRR process. Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au–B coupling bond, which considerably facilitates the hydrogenation of *N₂–*NH₃. The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process, utilizing boron clusters as reducing and stabilizing agents.