Electrochemical N₂ reduction provides a promising alternative to the Haber–Bosch process for sustainable ammonia production but enhancing its selectivity and activity remains a significant challenge. Here, this issue is tackled by triggering strong Lewis basicity within the catalyst, which boosts ambient ammonia synthesis from both thermodynamic and dynamic viewpoints. The enhanced π back donation induced by the Lewis base as the electron donor is first confirmed by first‐principle calculations, which greatly activates the NN bond and promotes its dissociation. Moreover, as suggested by molecular dynamics simulations, such abundant Lewis base would contribute to more surface heterogeneity and thus enhanced van der Waals interactions between nitrogen and the catalyst. Localized high concentration of N₂ molecules can be realized at the catalyst surface, enabling efficient N₂ delivery with a high flux and benefiting the following reaction process. As expected, the proof‐of‐concept metal‐free catalyst achieves a Faradaic efficiency of 62.9% and ammonia yield rate of 41.1 µg h⁻¹ mg⁻¹ at −0.2 V versus reversible hydrogen electrode. With this Lewis base‐assisted strategy, the superior efficiency would greatly reduce the energy loss of the system and cut down the fundamental cost, thus contributing to future practical applications.

中文翻译：

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在热力学和动态促进的固氮中揭示刘易斯碱的基本性质

电化学法将N ₂还原为Haber-Bosch工艺提供了有希望的替代方法，以实现可持续的氨生产，但是提高其选择性和活性仍然是一项重大挑战。在此，通过在催化剂内引发强路易斯碱性来解决该问题，从热力学和动力学角度来看，这都促进了周围氨的合成。由路易斯原理作为电子给体的感应增强的π背给定首先通过第一性原理计算得到证实，这大大激活了NN键并促进了其离解。而且，如分子动力学模拟所暗示的，这种丰富的路易斯碱将有助于更多的表面非均质性，并因此增强了氮与催化剂之间的范德华相互作用。局部高浓度氮可以在催化剂表面实现_2个分子，从而能够以高通量有效地输送N ₂，并有利于以下反应过程。正如预期的那样，与可逆氢电极相比，概念验证的无金属催化剂在-0.2 V时可达到62.9％的法拉第效率，氨产率为41.1 µg h ^-1 mg ^-1。使用这种Lewis基础辅助策略，卓越的效率将大大减少系统的能量损耗并降低基本成本，从而为将来的实际应用做出贡献。