Electrochemical N₂ reduction in aqueous solutions at ambient conditions is extremely challenging and requires rational design of electrocatalytic centers. We demonstrate a boron-doped graphene as an efficient metal-free N₂ reduction electrocatalyst. Boron doping in the graphene framework leads to redistribution of electron density, where the electron-deficient boron sites provide enhanced binding capability to N₂ molecules. Density functional theory calculations reveal the catalytic activities of different boron-doped carbon structures, in which the BC₃ structure enables the lowest energy barrier for N₂ electroreduction to NH₃. At a doping level of 6.2%, the boron-doped graphene achieves a NH₃ production rate of 9.8 μg·hr⁻¹·cm⁻² and one of the highest reported faradic efficiencies of 10.8% at −0.5 V versus reversible hydrogen electrode in aqueous solutions at ambient conditions. This work suggests the strong potential of atomic-scale design for efficient electrocatalysts for N₂ reduction.

在环境条件下水溶液中的电化学N ₂还原极具挑战性，需要合理设计电催化中心。我们证明了硼掺杂的石墨烯作为一种有效的无金属的N ₂还原电催化剂。石墨烯骨架中的硼掺杂导致电子密度的重新分布，其中缺电子的硼位点增强了与N ₂分子的结合能力。密度泛函理论计算揭示了不同掺杂硼的碳结构的催化活性，其中BC ₃结构使N ₂电还原为NH ₃的最低能垒。相对于可逆氢电极，在6.2％的掺杂水平下，硼掺杂的石墨烯的NH ₃产生速率为9.8μg·hr ^-1 ·cm ^-2，在-0.5 V时，报道的法拉第效率最高，为10.8％。在环境条件下的水溶液。这项工作表明原子尺度设计对于有效的N ₂还原电催化剂具有很大的潜力。