以金属卟啉作为催化剂的仿生催化氧化,是烃类化合物氧化的绿色催化新工艺.将金属卟啉固载形成多相催化体系,可以解决均相催化体系中金属卟啉易氧化分解或二聚而失活、回收困难等问题.综述了以氧化硅及改性氧化硅为载体的固载金属卟啉催化剂体系,介绍了硅胶及改性硅胶、介孔氧化硅、溶胶-凝胶法制备的氧化硅,以及氧化硅核壳磁性粒子为载体的固载金属卟啉催化剂.阐述了催化活性组分与载体之间的几种相互作用,如共价键、配位键、离子作用以及封装;分析了这些相互作用和载体的结构性能对催化剂催化性能的影响.对用溶胶-凝胶法构建有机-无机复合催化材料,以及以氧化硅核壳结构磁性粒子为载体的金属卟啉催化体系提出了展望.
Biomimetic catalytic oxidation using metalloporphyrins as catalysts is a new green process for catalytic oxidation of hydrocarbons.The heterogeneous catalytic processes with metalloporphyrins immobilization can solve the problems that result from homogeneous processes,such as catalyst deactivation due to the oxidative decomposition and dimerization of the metalloporphyrins.Furthermore,metalloporphyrins immobilization can help catalyst recycling.A review was provided in this paper about metalloporphyrins catalysts with silica and modified silica as support.Pure or modified silica gels,mesoporous silica,silica prepared by the sol-gel method,and core-shell magnetic particles covered with silica as matrixes were described in detail.Interactions between active component and the support,such as covalent binding,coordinative binding,ionic interactions,and entrapment were discussed.The sol-gel process to construct hybrid organic-inorganic catalytic materials,and the core-shell magnetic particles covered with silica as hopeful catalyst supports were prospected.
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