The production of ammonia under ambient conditions through electrocatalytic nitrogen reduction reaction is significant but challenging. The lack of an available active NRR electrocatalyst with a high selectivity impedes the development of the electrochemical ammonia synthesis. In this work, via first‐principles density functional theory calculations, we investigated various transition metal atoms (Fe, Cr, V, and Mo) substitution modified defective (with an oxygen vacancy) α‐MnO₂ (001) as NRR electrocatalyst. It was found that the incorporation of a single Mo atom substituent at Mn site of α‐MnO₂ (001) shows the best performance of nitrogen fixation through enzymatic mechanism with a favorable limiting potential of −0.14 V. The superior selectivity for NH₃ over H₂ is observed with high Faradaic efficiency of 99 %. The ‐like characteristics of occupied states around the Fermi level of Mo active center maximizes the p‐d orbital hybridization and thus promotes the stabilities of *N₂ and *N₂H, which leads to the superior NRR performance. These findings provide theoretical guidance to the development of highly efficient NRR electrocatalysts via defect engineering.

中文翻译：

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Mo原子修饰的有缺陷的α-MnO2的高性能固氮（001）

通过电催化氮还原反应在环境条件下产生氨是重要的，但是具有挑战性。缺少可用的具有高选择性的活性NRR电催化剂阻碍了电化学氨合成的发展。在这项工作中，通过第一原理密度泛函理论计算中，我们调查各种过渡金属原子（铁，铬，V和Mo）取代修饰有缺陷的（具有氧空位）α-MnO的₂（001）为NRR电催化剂。结果发现，在Mn位的单一的Mo原子取代基的掺入α-MnO的₂通过与NH -0.14 V的优良的选择性的有利限制了潜在的酶促机制固氮的（001）示出了最佳的性能₃观察到H ₂超过H ₂，法拉第效率高达99％。的 周围沫活性中心的费米能级被占状态的样特性最大化的p d轨道杂化，从而促进的* N的稳定性₂和* N ₂ H，这导致优良的NRR性能。这些发现为通过缺陷工程开发高效的NRR电催化剂提供了理论指导。