Single-Atom Low-Valent Alkaline-Earth-Metal Catalysts for Electrochemical Nitrogen Reduction with an Acceptance–Backdonation Mechanism

Single-atom catalysts (SACs) have drawn great attention in developing highly active and low-cost catalysts for electrocatalytic nitrogen reduction reaction (NRR) in ammonia synthesis, but the atomic metal centers are mainly limited to transition metals. Here, four stable alkaline-earth-metal (AEM)-based SACs are proposed by anchoring AEM on nitrogen-doped graphene nanoribbons, based on first-principles calculations. All SACs exhibit excellent NRR performance with competitive limiting potentials compared to stepped Ru (0001), and Ca-based SAC achieves optimal activity with a potential of −0.716 V. It is revealed that the low oxidation state of AEM is crucial for the activation of N₂ through an acceptance–backdonation mechanism. The antibonding 2π* orbital of N₂ can accept residual s electrons of low-valent AEM and backdonate electrons to the empty d orbitals of AEM, resulting in activation of N₂ molecules. In particular, the activation degree of N₂ and NRR activity is linearly associated with the charge states of AEMs. Our work reveals the underlying mechanism of AEMs for N₂ activation and reduction and presents the potential of AEM SACs as efficient electrochemical NRR catalysts.