Electrochemical N₂ fixation has gained much attention as an environmentally friendly and sustainable process for NH₃ production at ambient conditions. Its efficiency depends greatly on identifying highly active electrocatalysts with good stability. In this work, we propose the use of VO₂ hollow microspheres as a robust non‐precious metal catalyst for the N₂ reduction reaction (NRR). The catalyst operates efficiently and stably at neutral pH to high Faradaic efficiency (3.97 %) and NH₃ yield (14.85 μg h⁻¹ mg⁻¹_cat.) under an applied potential of −0.7 V (vs. the reversible hydrogen electrode). Note that this catalyst also presents a high selectivity for NH₃ synthesis without N₂H₄ generation. Density functional theory reveals that the energetically favorable pathway for NRR is *N₂→*NNH→*NHNH→*NHNH₂→*NH₂NH₂→*NH₂+NH₃→*NH₃+NH₃→2NH₃, where the first hydrogenation step to form *NNH is the potential‐determining step.

中文翻译：

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空心VO2微球在环境条件下的电催化固氮。

电化学固定N ₂作为在环境条件下生产NH _3的一种环境友好和可持续的过程已引起了广泛关注。其效率在很大程度上取决于鉴定具有良好稳定性的高活性电催化剂。在这项工作中，我们建议使用VO ₂空心微球作为N ₂还原反应（NRR）的坚固的非贵金属催化剂。该催化剂在中性pH值下可高效且稳定地运行至高法拉第效率（3.97％）和NH ₃收率（14.85μgh ^-1  mg ^-1 _cat）。）在-0.7 V的施加电势下（相对于可逆氢电极）。注意，该催化剂对NH ₃合成也具有高选择性，而没有生成N ₂ H ₄。密度泛函理论表明，NRR的能量有利途径为* N ₂ →* NNH→* NHNH→* NHNH ₂ →* NH ₂ NH ₂ →* NH ₂ + NH ₃ →* NH ₃ + NH ₃ →2NH ₃，其中形成* NNH的第一步是确定电位的步骤。