当前位置：
X-MOL 学术
›
J. Am. Chem. Soc.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
A Self-Assembled Cofacial Cobalt Porphyrin Prism for Oxygen Reduction Catalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-01-19 , DOI: 10.1021/jacs.6b12404
Amanda N. Oldacre 1 , Alan E. Friedman 1 , Timothy R. Cook 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-01-19 , DOI: 10.1021/jacs.6b12404
Amanda N. Oldacre 1 , Alan E. Friedman 1 , Timothy R. Cook 1
Affiliation
|
Herein we report the first study of the oxygen reduction reaction (ORR) catalyzed by a cofacial porphyrin scaffold accessed in high yield (overall 53%) using coordination-driven self-assembly with no chromatographic purification steps. The ORR activity was investigated using chemical and electrochemical techniques on monomeric cobalt(II) tetra(meso-4-pyridyl)porphyrinate (CoTPyP) and its cofacial analogue [Ru8(η6-iPrC6H4Me)8(dhbq)4(CoTPyP)2][OTf]8 (Co Prism) (dhbq = 2,5-dihydroxy-1,4-benzoquinato, OTf = triflate) as homogeneous oxygen reduction catalysts. Co Prism is obtained in one self-assembly step that organizes six total building blocks, two CoTPyP units and four arene-Ru clips, into a cofacial motif previously demonstrated with free-base, Zn(II), and Ni(II) porphyrins. Turnover frequencies (TOFs) from chemical reduction (66 vs 6 h-1) and rate constants of overall homogeneous catalysis (kobs) determined from rotating ring-disk experiments (1.1 vs 0.05 h-1) establish a cofacial enhancement upon comparison of the activities of Co Prism and CoTPyP, respectively. Cyclic voltammetry was used to initially probe the electrochemical catalytic behavior. Rotating ring-disk electrode studies were completed to probe the Faradaic efficiency and obtain an estimate of the rate constant associated with the ORR.
中文翻译：
用于氧还原催化的自组装共面钴卟啉棱镜
在此，我们报告了使用配位驱动的自组装而无需色谱纯化步骤以高产率（总体为 53%）获得的共面卟啉支架催化的氧还原反应 (ORR) 的首次研究。使用化学和电化学技术对单体四（内消旋-4-吡啶基）卟啉钴（CoTPyP）及其表面类似物[Ru8(η6-iPrC6H4Me)8(dhbq)4(CoTPyP)2][ OTf]8 (Co Prism) (dhbq = 2,5-dihydroxy-1,4-benzoquinato, OTf = triflate) 作为均相氧还原催化剂。Co Prism 是在一个自组装步骤中获得的，该步骤将六个总构建块、两个 CoTPyP 单元和四个芳烃-Ru 夹子组织成先前用游离碱、Zn(II) 和 Ni(II) 卟啉演示的共面图案。来自化学还原（66 对 6 h-1）的转换频率（TOF）和从旋转环盘实验（1.1 对 0.05 h-1）确定的整体均相催化（kobs）的速率常数在比较活性时建立了共面增强分别是 Co Prism 和 CoTPyP。循环伏安法用于初步探测电化学催化行为。完成旋转环盘电极研究以探测法拉第效率并获得与 ORR 相关的速率常数的估计值。
更新日期：2017-01-19
中文翻译：
用于氧还原催化的自组装共面钴卟啉棱镜
在此，我们报告了使用配位驱动的自组装而无需色谱纯化步骤以高产率（总体为 53%）获得的共面卟啉支架催化的氧还原反应 (ORR) 的首次研究。使用化学和电化学技术对单体四（内消旋-4-吡啶基）卟啉钴（CoTPyP）及其表面类似物[Ru8(η6-iPrC6H4Me)8(dhbq)4(CoTPyP)2][ OTf]8 (Co Prism) (dhbq = 2,5-dihydroxy-1,4-benzoquinato, OTf = triflate) 作为均相氧还原催化剂。Co Prism 是在一个自组装步骤中获得的，该步骤将六个总构建块、两个 CoTPyP 单元和四个芳烃-Ru 夹子组织成先前用游离碱、Zn(II) 和 Ni(II) 卟啉演示的共面图案。来自化学还原（66 对 6 h-1）的转换频率（TOF）和从旋转环盘实验（1.1 对 0.05 h-1）确定的整体均相催化（kobs）的速率常数在比较活性时建立了共面增强分别是 Co Prism 和 CoTPyP。循环伏安法用于初步探测电化学催化行为。完成旋转环盘电极研究以探测法拉第效率并获得与 ORR 相关的速率常数的估计值。
京公网安备 11010802027423号