Electrochemical nitrogen reduction reaction (NRR) is becoming increasingly important for ammonia (NH₃) synthesis, but the development of effective electrocatalysts remains a great challenge. Here, by means of extensive first-principles calculations, we systematically study the potential of coronene-based two-dimensional (2D) metal–organic frameworks (TM–PTC, TM = Fe, Sc, Ti, V, Cr, Mn, Co, Ni, Cu) as single-atom catalysts for dinitrogen (N₂) fixation. Our results show that the gas phase N₂ can be readily reduced to NH₃ on V/Fe–PTC through the enzymatic/distal mechanism with a quite low overpotential of 0.60/0.53 V. The underlying physics for the excellent NRR performance is discussed in detail. Moreover, the competing reaction of hydrogen evaluation reaction (HER) is dramatically suppressed in Fe–PTC, endowing them with high selectivity and thus rendering them ideal for NH₃ synthesis. This work not only provides efficient electrocatalysts for NRR under mild reaction conditions but also helps guide the future development of single-atom electrocatalysts.

中文翻译：

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基于 Coronene 的 2D 金属-有机框架：用于氮还原反应的新系列单原子催化剂

电化学氮还原反应 (NRR) 对于氨 (NH ₃ ) 合成变得越来越重要，但开发有效的电催化剂仍然是一个巨大的挑战。在这里，通过广泛的第一性原理计算，我们系统地研究了基于晕苯的二维 (2D) 金属有机骨架 (TM-PTC, TM = Fe, Sc, Ti, V, Cr, Mn, Co , Ni, Cu) 作为用于固定二氮 (N ₂ ) 的单原子催化剂。我们的结果表明，气相 N ₂可以很容易地还原为 NH ₃在 V/Fe-PTC 上通过酶促/远端机制，具有 0.60/0.53 V 的相当低的过电位。详细讨论了优异 NRR 性能的基础物理。此外，Fe-PTC中氢评价反应（HER）的竞争反应被显着抑制，赋予它们高选择性，从而使其成为NH ₃合成的理想选择。这项工作不仅在温和的反应条件下为 NRR 提供了高效的电催化剂，而且有助于指导单原子电催化剂的未来发展。