金属卟吩作为氧还原的电催化剂。

Metal corroles as electrocatalysts for oxygen reduction.

作者信息

Collman James P, Kaplun Marina, Decréau Richard A

机构信息

Department of Chemistry, Stanford University, Stanford, CA 94305, USA.

出版信息

Dalton Trans. 2006 Jan 28(4):554-9. doi: 10.1039/b512982f. Epub 2005 Nov 2.

Abstract

The rotating ring disk electrode method has been used to study O2 electroreduction with metal corroles. Catalysis begins at potentials that are 0.5-0.7 V more positive than the expected potential of the M(III/II) couple based on studies in non-aqueous solutions. The path of O2 reduction depends on the nature of the metal ion. Cobalt corroles promote O2 reduction to H2O2. Iron corroles catalyse O2 reduction via parallel two- and four-electron pathways, with a predominate four-electron reaction. The rate constants for the individual O2 reduction paths are given at pH 7. Mechanisms are proposed on the basis of pH dependence, inhibition studies, and Tafel slopes. An imidazole-tailed iron corrole catalyses H2O2 disproportionation analogous to catalase.

摘要

旋转环盘电极法已被用于研究金属卟吩对O2的电还原作用。基于在非水溶液中的研究,催化作用始于比M(III/II)电对预期电位更正0.5 - 0.7 V的电位。O2还原的路径取决于金属离子的性质。钴卟吩促进O2还原为H2O2。铁卟吩通过平行的双电子和四电子途径催化O2还原,以四电子反应为主。在pH 7时给出了各个O2还原路径的速率常数。基于pH依赖性、抑制研究和塔菲尔斜率提出了反应机理。一种咪唑尾铁卟吩催化H2O2歧化反应,类似于过氧化氢酶。

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