Rosenthal Joel, Nocera Daniel G
Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
Acc Chem Res. 2007 Jul;40(7):543-53. doi: 10.1021/ar7000638. Epub 2007 Jun 27.
The selective reduction of oxygen to water requires four electrons and four protons. The design of catalysts that promote oxygen reduction therefore requires the management of both electron and proton inventories. Pacman and Hangman porphyrins provide a cleft for oxygen binding, a redox shuttle for oxygen reduction, and functionality for tuning the acid-base properties of bound oxygen and its intermediates. With proper control of the proton-coupled electron transfer events, O-O bond breaking of oxygen, and more generally oxygenated substrates, may be achieved with high efficiencies. The rule set developed for oxygen reduction may be applied to a variety of other small molecule activation reactions of consequence to energy conversion.
将氧气选择性还原为水需要四个电子和四个质子。因此，设计促进氧还原的催化剂需要同时管理电子和质子库存。Pacman和Hangman卟啉为氧结合提供了一个裂缝，为氧还原提供了一个氧化还原穿梭体，并具有调节结合氧及其中间体酸碱性质的功能。通过适当控制质子耦合电子转移事件，可以高效地实现氧的O-O键断裂，更普遍地说，也可以实现氧化底物的O-O键断裂。为氧还原制定的规则集可应用于能量转换中其他各种重要的小分子活化反应。
