Crystal structures of molybdenum borides dictate electrocatalytic ammonia synthesis efficiency

Rather than multivalence molybdenum (Mo), the low valence Mo has rarely been reported as active site for nitrogen reduction. Herein, molybdenum borides with various Mo-B stoichiometry ratios (Mo₂B, α-MoB, and Mo₂B₄) in which Mo shows low valence (<1) are synthesized as electrochemical nitrogen reduction reaction (eNRR) catalysts. Mo₂B₄ demonstrates the highest NH₃ yield of 7.65 µg h^{− 1}/mg at − 0.15 V with Faradaic efficiency (FE) of 12.47 %, while α-MoB exhibits the fastest intrinsic eNRR reaction rate with a higher FE of 17.17 % after considering electrochemically active surface area. DFT calculations reveal that both enzymatic and consecutive mechanisms via side-on configuration can proceed on α-MoB. Additionally, α-MoB exhibits suppressed HER activity due to an optimal surface B occupancy. The eNRR of molybdenum borides were verified qualitatively and quantitatively by ¹⁵N₂ isotope experiments. This study demonstrated a synergistic design of eNRR and HER activity to achieve efficient electrocatalytic ammonia production with high eNRR selectivity. © 2023 Elsevier B.V.