金属-有机骨架材料在催化氧化反应中的应用

Metal-Organic Frameworks for Catalytic Oxidation

本文综述了近几年金属-有机骨架(metal-organic frameworks,MOFs)材料在催化氧化反应中的研究进展。由于MOFs材料在结构上常具有特殊活性位点、孔隙率高、比表面积大且孔尺寸与性质可调等特点,在催化上有极大的应用潜力。本文主要介绍了MOFs材料自身作为催化剂和其作为载体负载具有催化活性组分的催化氧化反应。其中,着重介绍了具有配位不饱和金属位点的MOFs和MOFs做为载体负载金属纳米颗粒、多金属氧酸盐和金属卟啉用于催化的氧化反应,包括一些有机分子如烷烃、苄基化合物、烯烃、醇、酚、硫化物和无机小分子CO、水的催化氧化,也介绍了相关仿生催化和有机染料的催化氧化。MOFs和MOFs载体的催化性能主要从稳定性、非均相性、尺寸选择性及活性位的析出四个方面进行了评价。同时,对MOFs材料在催化应用中的发展趋势作了展望。

The use of metal-organic frameworks（ MOFs） as heterogeneous catalyst for oxidation reactions developed in recent years is reviewed. Because of their unique structural features and outstanding physical /chemical properties,including metal or organic active sites in pore surface,high porosity,large surface areas,and tailorable pore properties,MOFs are promising and favorable for application in various catalytic reactions. In this review,the applications of MOFs in catalytic oxidation as catalysts or as supports of catalytic active species are discussed. Catalytic MOFs with coordinatively unsaturated metal active sites and MOFs supported metal nanoparticles（ MNPs）,polyoxometalates（ POMs）,and metalloporphyrins are emphasized. Catalytic oxidization of varieties of organic molecules,including alkanes,benzylic hydrocarbons,olefins,alcohols,phenols,and sulfur compounds,as well as small inorganic molecules,including CO and water in MOFs and/or MOFs supported catalysts are summarized. In addition,the application of MOFs in the oxidation of organic dyes and biomimetic catalysis is also discussed. Catalytic performances of these MOFs and MOFs supported catalysts are evaluated from the stability,heterogeneity,and shape/size selectivity,as well as precipitation of the active species aspects. Finally,the development trend of MOFs in the catalytic applications is prospected.