The electrochemical reduction reaction of dinitrogen into ammonia (eNRR) has been considered as one of the most promising candidates to replace the traditional Haber-Bosch process. By using the density functional theory calculations, 20 kinds of atomically dispersed tri-atoms supported on graphdiyne monolayer catalysts M_xM′_yM″_3-x-y/GDY (M, M′, M″ = Cr, Mo, W, Fe) were investigated for the eNRR process. It is found that Cr₃/GDY, W₃/GDY, and Cr₂Mo₁/GDY exhibit high stability, selectivity, and activity, with limiting potentials of only −0.36, −0.35, and −0.29 V, respectively. Specifically, by further investigating the most active and exemplar Cr₂Mo₁/GDY system, in the presence of N₂ adsorption on the catalyst, it would promote the desorption of the final product NH₃. More importantly, by evaluating the growth energy of the supported atomic metal centers, these catalysts have a very broad theoretical energy window, indicating their possibility of synthesizing. These atomically dispersed metal centers cooperating with the GDY monolayer could promote the multi-step protonation process. Our findings shed light on the rational and precise design of novel catalysts for electrochemical energy conversion and storage.

双氮电化学还原反应生成氨 (eNRR) 被认为是最有希望取代传统哈伯-博世工艺的候选方法之一。通过密度泛函理论计算，20种原子分散的三原子负载在石墨二炔单层催化剂上M _x M' _y M″ _3-xy /GDY (M, M', M″ = Cr, Mo, W, Fe)对 eNRR 过程进行了调查。结果表明，Cr ₃ /GDY、W ₃ /GDY和Cr ₂ Mo ₁ /GDY表现出高稳定性、选择性和活性，极限电位分别仅为-0.36、-0.35和-0.29 V。具体来说，通过进一步研究最活跃和典型的 Cr ₂Mo ₁ /GDY体系在催化剂上吸附N ₂的情况下，会促进最终产物NH ₃的解吸。更重要的是，通过评估负载原子金属中心的生长能量，这些催化剂具有非常宽的理论能量窗口，表明它们具有合成的可能性。这些原子分散的金属中心与 GDY 单层配合可以促进多步质子化过程。我们的研究结果阐明了用于电化学能量转换和存储的新型催化剂的合理和精确设计。