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Exploring electrocatalysts with high activity is essential for the production of ammonia via an electrochemical routine. By employing density functional theory calculations, we investigated the electrochemical nitrogen reduction reaction (eNRR) activity on binary metal borides, a model system of metal borides. To elaborate the mechanisms, molybdenum borides (Mo2B, α-MoB, and MoB2) were first modeled; the results indicate that the crystal structures greatly impact the N2 adsorption and therefore the electrocatalytic activity. Our electronic structure investigation suggests that boron p-orbital hybrids with dinitrogen π*-orbital, and the population on p−π*-orbital determine the N2 adsorption strength. Therefore, the isolated boron site of Mo2B with less filled pz-orbital benefits the activation of N2 and weaken the triple bond of dinitrogen. This isolated boron sites concept was successfully extended to other metal borides in the form of M2B (M stands for Ti, Cr, Mn, Fe, Co, Ni, Ta, W). Mo2B, Fe2B, and Co2B were discovered as the most promising candidates with low limiting potentials due to appropriate adsorption strength of reaction intermediates led by moderate pz filling. This work provides insights for designing metal borides as promising eNRR electrocatalysts.
Liu et al. (Thu,) studied this question.