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近年来,催化氧化去除有机污染物受到越来越多的重视,但是氧气或过氧化氢绿色催化剂的使用因O—O键活化的效率低下而受到限制.本文综述了不同种类氧化酶和加氧酶包括以多铜原子为中心(MCOs,如漆酶)和以卟啉/非卟啉铁为中心(HCOs,如细胞色素P450酶等)的氧化酶和加氧酶的O—O键活化机理.前者活性中心以4个铜原子组成,与其结合的氧气分子通过4电子过程实现O—O键断裂;后者主要以单个铁原子为活性中心,与铁配位的基团及铁的配合状态决定与其结合的氧气或过氧化氢分子中O—O键断裂机理.同时本文也对仿生催化材料在O—O键活化方面的工作进行了综述,其中主要包括对酶催化活性中心的模拟和支撑材料的选择.本综述旨在为O—O键活化的仿生催化剂设计和环境应用提供参考.
In recent years, more and more attention has been paid to the catalytic oxidation to remove organic pollutants, but the use of oxygen or hydrogen peroxide green catalyst is limited by the inefficiency of O-O activation.In this paper, different kinds of oxidase and oxygenation Enzymes include the O-O activation mechanism of oxidases and oxygenases, which are centered on copper ions (MCOs such as laccase) and centered on porphyrin / non-porphyrin iron (HCOs such as cytochrome P450 enzymes) . The former active center is composed of four copper atoms, the oxygen molecules combined with it are O-O bond breaking through four-electron process. The latter mainly takes a single iron atom as the active center, and the coordination state with iron and the coordination state of iron And determine the O-O bond breaking mechanism in oxygen or hydrogen peroxide molecules combined with it.The work of biomimetic catalytic materials on the activation of O-O bonds is also reviewed in this paper, including the simulation and support of the active catalytic center Material Selection This review is intended to provide a reference for the design of biomimetic catalysts for O-O bond activation and environmental applications.