Departments of †Chemical Engineering, ‡Materials Science and Engineering, and §Chemistry, Carnegie Mellon University , 5000 Forbes Avenue, Pittsburgh, Pennsylvania 15213, United States.
J Am Chem Soc. 2014 Apr 16;136(15):5603-6. doi: 10.1021/ja5015986. Epub 2014 Apr 7.
Iron complexes of tetra-amido macrocyclic ligands are important members of the suite of oxidation catalysts known as TAML activators. TAML activators are known to be fast homogeneous water oxidation (WO) catalysts, producing oxygen in the presence of chemical oxidants, e.g., ceric ammonium nitrate. These homogeneous systems exhibited low turnover numbers (TONs). Here we demonstrate immobilization on glassy carbon and carbon paper in an ink composed of the prototype TAML activator, carbon black, and Nafion and the subsequent use of this composition in heterogeneous electrocatalytic WO. The immobilized TAML system is shown to readily produce O2 with much higher TONs than the homogeneous predecessors.
四氨大环配体的铁配合物是被称为 TAML 激活剂的氧化催化剂系列中的重要成员。TAML 激活剂是众所周知的快速均相水氧化 (WO) 催化剂,在化学氧化剂(如硝酸铈铵)存在下产生氧气。这些均相体系的转化率(TON)较低。在这里,我们证明了在由原型 TAML 激活剂、炭黑和 Nafion 组成的油墨中在玻璃碳和碳纸上的固定化,以及随后在非均相电催化 WO 中使用这种组合物。所固定的 TAML 体系被证明能够很容易地产生 O2,其 TON 比均相前体高得多。