Bimetal‐Doped Boron Nitride Electrocatalyst for Nitrogen Reduction Reaction: A Theoretical Design

ABSTRACT The electrocatalytic nitrogen reduction reaction (NRR) is a green, low‐energy alternative to the Haber‐Bosch process. This study constructed dual unsaturated vacancies on a stable B ₄ N ₄ monolayer and designed a B ₃ N ₄ substrate. The calculation shows that the B ₃ N ₄ structure has a great stability. The dual atom catalysts (DACs) were constructed through bimetallic doping, denoted as TM ₁ TM ₂ @B ₃ N ₄ , for the NRR using a theoretical high‐throughput screening integrated with density functional theory (DFT) calculations. The electrocatalytic NRR performance of the 91 designed DACs was systematically investigated. 4 heteronuclear systems CrZr@B ₃ N ₄ , CrHf@B ₃ N ₄ , MnNb@B ₃ N ₄ , and FeMo@B ₃ N ₄ were screened out, which are promising NRR electrocatalysts with excellent NRR activities and selectivities using a 3+1 screening strategy. Notably, the designed CrZr@B ₃ N ₄ demonstrates an outstanding performance with a low limiting potential of −0.16 V along the mixed pathway. Furthermore, a Cascading Associative‐Dissociative (Cascading A–D) reaction mechanism is proposed in which N─N bond scission takes place immediately after the second proton‐coupled electron transfer step ( ^* N ₂ H + H ⁺ + e ⁻ → ^* NH ^* NH). This reaction mechanism was only observed in eight designed electrocatalysts with relatively low activities. This work provides a rational framework for designing high‐performance NRR catalysts and efficient ammonia synthesis.