Electrochemical nitrogen fixation via a convenient and sustainable manner, exhibits an intriguing prospect for ammonia generation under ambient conditions. Currently, the design and development of high-efficiency and low-cost electrocatalysts remains the major challenge confronting nitrogen reduction reaction (NRR). Herein, anchoring the single Mo atom on the C₉N₄ substrate (Mo@C₉N₄) to form an efficient single-atom catalyst (SAC) is proposed for the conversion of N₂ to NH₃. By employing density functional theory (DFT) calculations, we demonstrated that gas phase N₂ can be sufficiently activated and efficiently reduced to NH₃ on the surface of Mo@C₉N₄. Meanwhile, we found that the NRR dominantly occurred on the Mo center via a preferred distal pathway with favorable limiting potential of 0.40 V. Importantly, the as-established Mo@C₉N₄ catalyst exhibits an outstanding structural stability and good selectivity toward NRR. These findings provide a promising platform for designing Mo-based SACs for electrochemical N₂ fixation.

通过便利和可持续的方式进行电化学固氮，在环境条件下产生氨的前景诱人。当前，高效和低成本电催化剂的设计和开发仍然是氮还原反应（NRR）面临的主要挑战。在此，提出了将单个Mo原子锚定在C ₉ N ₄衬底（Mo @ C ₉ N ₄）上以形成有效的单原子催化剂（SAC）以将N ₂转化为NH _3的方法。通过使用密度泛函理论（DFT）计算，我们证明了气相N ₂可以被充分活化并有效地还原为NH ₃在Mo @ C ₉ N ₄的表面上。同时，我们发现NRR主要通过优选的远端路径以0.40 V的有利极限电位在Mo中心发生。重要的是，已确立的Mo @ C ₉ N ₄催化剂具有出色的结构稳定性和对NRR的良好选择性。这些发现为设计用于电化学N ₂固定的基于Mo的SAC提供了有希望的平台。