Electrocatalytic Reduction of Oxygen by Cofacial Porphyrin

面卟啉电催化还原氧

• 批准号: 06044256
• 负责人: OSUKA Atsuhiro
• 金额: --
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Overseas Scientific Survey.
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06044256/
• 关键词: Diporphyrin; Oxygen Reduction; Cobalt Porphyrin; Electroreduction

1,2-Phenylene-bridged dicobalt diporphyrin 1 catalyzed efficiently the four-electron reduction of dioxygen to water in acidic solution. The catalytic activity of the dioxygen is strongly affected by the substitutents on the phenyl rings attached to the porphyrin macrocycles. Namely, the Koutecky-Levich plot of (limiting current)^<-1> vs (rotation rate)^<-1/2> confirms that the four electron pathway is the major for the dioxygen reduction : the number of the electrons consumed in the process determined from the slop of the polt is 3.8, while similar analysis indicates the numbers of electrons in the corresponding reduction reaction of 2 and 3 are 1.9 and 2.7, respectively. Thus, we have revealed that such a subtle structural perturbation on the porphyrin catalysts leads to significant change in the reduction pathway.

在酸性条件下，1，2-苯基桥联双钴双卟啉1能有效地催化氧四电子还原成水。大环上苯环上的取代基对氧的催化活性有很大影响。也就是说，(极限电流)^&lt；-1&gt；对(转速)^&lt；-1/2&gt；的Koutecky-Levich图证实了四个电子路径是氧气还原的主要途径：由极斜率确定的过程中消耗的电子数为3.8，而类似的分析表明相应的还原反应2和3中的电子数分别为1.9和2.7。因此，我们揭示了卟啉催化剂上的这种微妙的结构扰动导致了还原途径的显著变化。

项目成果

Shigeki Kawabata: "A Convenient Synthesis of Polyynebridged Porphyrin Dimers" Chemistry Letters. 1994. 1797-1800 (1994)

Shigeki Kawabata：“聚炔桥卟啉二聚体的便捷合成”化学快报。

Gil Jae Park: "Electrocatalytic Four-Electron Reduction of Dioxygen by 1,2-Phenylene-Bridged Dicobalt Diporphyrins" Chemistry Letters. 1995(印刷中). (1995)

Gil Jae Park：“1,2-亚苯基桥联二钴二卟啉的电催化四电子还原”化学快报 1995（出版中）。

Atsuhiro Osuka: "Picosecond Excited State Dynamics of Fixed Distance Triads Consisting of Metalloporphyrin,Doubly Strapped Metal-Free Porphyrin,and Pyromellitimide" Chem.Phys.Lett.225. 140-145 (1994)

Atsuhiro Osuka：“由金属卟啉、双带金属卟啉和均苯四酰亚胺组成的固定距离三元组的皮秒激发态动力学”Chem.Phys.Lett.225。

Gil Jae Park: "Electrocatalytic Four-Electron Reduction of Dioxygen by 1,2-Phenylene-Bridged Dicobalt Diporphyrins" Chemistry Letters. 1995 (in press). (1995)

Gil Jae Park：“1,2-亚苯基桥联二钴二卟啉对双氧的电催化四电子还原”化学快报。