Molecular catalysts can promote ammonia oxidation, providing mechanistic insights into the electrochemical N₂ cycle for a carbon-free fuel economy. We report the ammonia oxidation activity of carbon anodes functionalized with the oligomer {[Ru^II(bda-κ-N²O²)(4,4′-bpy)]₁₀(4,4′-bpy)}, Rubda-10, where bda is [2,2′-bipyridine]-6,6′-dicarboxylate and 4,4′-bpy is 4,4′-bipyridine. Electrocatalytic studies in propylene carbonate demonstrate that the Ru-based hybrid anode used in a 3-electrode configuration transforms NH₃ to N₂ and H₂ in a 1:3 ratio with near-unity faradaic efficiency at an applied potential of 0.1 V vs Fc^+/0, reaching turnover numbers of 7500. X-ray absorption spectroscopic analysis after bulk electrolysis confirms the molecular integrity of the catalyst. Based on computational studies together with electrochemical evidence, ammonia nucleophilic attack is proposed as the primary pathway that leads to critical N–N bond formation.

中文翻译：

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通过 CH-π 相互作用锚定在石墨电极上的 Ru-bda 低聚物进行多相电化学氨氧化

分子催化剂可以促进氨氧化，为无碳燃料经济性的电化学 N ₂循环提供机理见解。^{我们报告了用低聚物 {[Ru II} (bda-κ- N ² O ² )(4,4'-bpy)] ₁₀ (4,4'-bpy)}、Rubda-10功能化的碳阳极的氨氧化活性，其中 bda 是 [2,2'-联吡啶]-6,6'-二羧酸盐，4,4'-bpy 是 4,4'-联吡啶。碳酸亚丙酯的电催化研究表明，在 3 电极配置中使用的基于 Ru 的混合阳极将 NH ₃转化为 N ₂和 H ₂在 1:3 的比例下，法拉第效率在 0.1 V vs Fc ^+/0的应用电位下接近统一，达到 7500 的周转数。本体电解后的 X 射线吸收光谱分析证实了催化剂的分子完整性。基于计算研究和电化学证据，氨亲核攻击被认为是导致关键 N-N 键形成的主要途径。