Fast Water Oxidation Using Iron

作者：W. Chadwick Ellis, Neal D. McDaniel, Stefan Bernhard, Terrence J. Collins · 发表于：Journal of the American Chemical Society · 年份：2010 · DOI：10.1021/ja104766z · 被引用次数：619 · 研究领域：Metal-Catalyzed Oxygenation Mechanisms、Electrocatalysts for Energy Conversion、Metal complexes synthesis and properties

Photolysis of water, a long-studied strategy for storing solar energy, involves two half-reactions: the reduction of protons to dihydrogen and the oxidation of water to dioxygen. Proton reduction is well-understood, with catalysts achieving quantum yields of 34% when driven by visible light. Water oxidation, on the other hand, is much less advanced, typically involving expensive metal centers and rarely working in conjunction with a photochemically powered system. Before further progress can be made in the field of water splitting, significant developments in the catalysis of oxygen evolution are needed. Herein we present an iron-centered tetraamido macrocyclic ligand (Fe-TAML) that efficiently catalyzes the oxidative conversion of water to dioxygen. When the catalyst is combined in unbuffered solution with ceric ammonium nitrate, its turnover frequency exceeds 1.3 s(-1). Real-time UV-vis and oxygen monitoring of the active complex give insights into the reaction and decay kinetics.