Li Jun, Shi Xiaohuo, Zhang Feiyang, Lu Xingyu, Zhang Yaqiong, Liao Rongzhen, Zhang Biaobiao
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310058, China.
Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou, Zhejiang 310024, China.
JACS Au. 2025 Apr 15;5(4):1812-1821. doi: 10.1021/jacsau.5c00054. eCollection 2025 Apr 28.
Molecular catalysts for the electrocatalytic ammonia oxidation reaction (eAOR) have much to offer in terms of mechanistic investigations and practical energy issues. This work reports the use of complex [Ru(pdc-κ-NO)(bpy)(NH)] ( ) (Hpdc = 2, 6-pyridinedicarboxylic acid; bpy = 2,2'-bipyridine) bearing a readily accessible pdc ligand to catalyze ammonia oxidation under electrochemical conditions. The rich structural variations of in coordinating solvents and an ammonia atmosphere were fully characterized by cyclic voltammograms (CVs), NMR, and XRD. CV experiments showed that promotes electrocatalytic ammonia oxidation at a low overpotential of 0.85 V with a calculated catalytic rate ( ) of 18.9 s. Controlled potential electrolysis (CPE) at an applied potential of 0.3 V vs Fc achieves 76.1 equiv of N with a faradaic efficiency of 89.8%. Experimental and computational analyses indicated that oxidation of generates a reactive intermediate, which undergoes sequential electron and proton transfer steps to form a species. N-N bond formation occurs via the nucleophilic attack of an ammonia molecule on the moiety with a facile barrier of 8.6 kcal/mol. Eventually, N evolved as the product after releasing two electrons and three protons.
用于电催化氨氧化反应（eAOR）的分子催化剂在机理研究和实际能源问题方面有很大的贡献。这项工作报道了使用带有易于获得的pdc配体的配合物[Ru(pdc-κ-NO)(bpy)(NH)]（ ）（Hpdc = 2,6 - 吡啶二甲酸；bpy = 2,2'-联吡啶）在电化学条件下催化氨氧化。通过循环伏安图（CVs）、核磁共振（NMR）和X射线衍射（XRD）对 在配位溶剂和氨气氛中的丰富结构变化进行了全面表征。CV实验表明， 在0.85 V的低过电位下促进电催化氨氧化，计算得到的催化速率（ ）为18.9 s⁻¹。相对于Fc在0.3 V的外加电位下进行控制电位电解（CPE），得到76.1当量的N₂，法拉第效率为89.8%。实验和计算分析表明， 的氧化产生了一个活性 中间体，该中间体经过连续的电子和质子转移步骤形成一个 物种。N - N键的形成是通过氨分子对 部分的亲核攻击发生的，其势垒为8.6 kcal/mol。最终，N₂在释放两个电子和三个质子后作为产物析出。
