High-throughput screening of B/N-doped graphene supported single-atom catalysts for nitrogen reduction reaction

Abstract

Transitional metal single atom (TM₁) doped graphene catalysts have been widely applied in electrochemical N₂ reduction reaction (NRR). However, it remains a challenge for the rational design of highly active and selective electrocatalysts owing to limited knowledge of structure-activity correlations. Here, we adopted first-principle calculations to high-throughput screen the NRR performance of TM₁ coordinated with two boron and two nitrogen atoms in graphene (TM₁-B₂N₂/G). A “five-step” strategy was implemented by progressively considering different metrics such as stability, N₂ adsorption, N₂ activation, potential-determining step, and selectivity. As a result, a volcano plot of reactivity is established by using the valence electron number of TM₁ as the descriptor. Among all catalysts, Cr₁-B₂N₂/G exhibits superior performance with a limiting potential of -0.43 V with high selectivity of NRR interpreted by better spatial symmetry and excellent compatibility in terms of energy when N₂ interacts with TM₁. Our work reveals the general strategy of computational efforts to predict the next generation of advanced catalytic materials for NRR.

Keywords

Single-atom catalysts / ammonia synthesis / density functional theory / structure-activity relationship / descriptor

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