Abstract The nitrogen reduction reaction (NRR) under ambient conditions is still challenging due to the inertness of N2. Herein, we report a series of superior NRR catalysts identified by examining Ti2NO2 MXenes embedded with 28 different single-atom catalysts using first-principles calculations. The stability of this system was first verified using formation energies, and it is discovered that N2 can be effectively adsorbed due to the synergistic effect between single atom catalysis and the Ti atoms. Examination of the electronic structure demonstrated that this design satisfies orbital symmetry matching where “acceptor-donor” interaction scenario can be realized. A new “enzymatic-distal” reaction mechanism that is a mixture of the enzymatic and distal pathways was also discovered. Among all of the candidates, Ni anchored on MXene system achieves an onset potential as low as −0.13 V, which to the best of our knowledge is the lowest onset potential value reported to date. This work elucidates the significance of orbital symmetry matching and provides theoretical guidance for future studies.

中文翻译：

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轨道对称匹配：实现优于锚定在 Mxene 底物上的单原子催化剂的氮还原反应

摘要 由于 N2 的惰性，环境条件下的氮还原反应 (NRR) 仍然具有挑战性。在此，我们报告了通过使用第一性原理计算检查嵌入 28 种不同单原子催化剂的 Ti2NO2 MXenes 确定的一系列优质 NRR 催化剂。该系统的稳定性首先通过形成能得到验证，发现由于单原子催化与 Ti 原子之间的协同作用，N2 可以被有效吸附。对电子结构的检查表明，该设计满足轨道对称匹配，其中可以实现“受体-供体”相互作用场景。还发现了一种新的“酶促-远端”反应机制，即酶促和远端途径的混合。在所有候选人中，锚定在 MXene 系统上的 Ni 实现了低至 -0.13 V 的起始电位，据我们所知，这是迄今为止报道的最低起始电位值。这项工作阐明了轨道对称匹配的重要性，并为未来的研究提供了理论指导。