The electrocatalytic nitrogen reduction reaction (NRR) for NH₃ synthesis is still far from being practical and competitive with the common Haber–Bosch process. The rational design of highly selective NRR electrocatalyst is therefore urgently needed, which requires a deep understanding of both the electrode–electrolyte interface and the mass transport of reactants. Here, we develop a theoretical framework that includes electric double layer (EDL), mass transport, and the NRR kinetics. This allows us to evaluate the roles of near-electrode environment and N₂ diffusion on the NRR selectivity and activity. The EDL, as the immediate reaction environment, remarkably impedes the diffusion of N₂ to the cathode surface at high electrode potentials, which explains experimental observations. This article also gives microscopic insights into the interplay between N₂ diffusion and reaction activity under the nano-confinement, providing theoretical guidance for future design of advanced NRR electrocatalytic systems.

中文翻译：

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通过定制双电层增强电催化 N2 还原

_{用于 NH 3}合成的电催化氮还原反应 (NRR)与常见的 Haber-Bosch 工艺相比，还远没有实用性和竞争力。因此，迫切需要合理设计高选择性 NRR 电催化剂，这需要对电极-电解质界面和反应物的传质有深入的了解。在这里，我们开发了一个理论框架，包括双电层 (EDL)、质量传输和 NRR 动力学。这使我们能够评估近电极环境和 N ₂扩散对 NRR 选择性和活性的作用。EDL作为直接反应环境，显着阻碍了N _2的扩散在高电极电位下到阴极表面，这解释了实验观察。本文还对纳米约束下N _{2扩散与反应活性之间的相互作用进行了微观洞察，为未来设计先进的NRR电催化系统提供了理论指导。}