摘要
Engineering metal-organic frameworks（MOF） for heterogeneous catalysts have been of extreme interest since they have large pore size within the crystalline framework and well defined pore architecture. Ni-containing MOF Ni2（3,5-Pydc）2（H2O）8·2H2O（1·H2O） was prepared by solvothermal method from 3,5-pyridinedicarboxylic acid, D-camphoric acid and Ni（NO3）2·6H2O in dimethylformamide（DMF）/water（volume ratio 2：1）. And two gold and silver functionalized 1·H2O catalysts were prepared by impregnation method. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF were in-depth characterized by single crystal X-ray diffraction, powder X-ray diffraction（PXRD）, thermogravimetric analysis（TGA）, transmission electron microscopy（TEM）, and inductively coupled plasma-atomic emission spectroscopy（ICP-AES）. Their catalytic performance was examined in one-pot synthesis of structurally divergent propargylamines via three component coupling of aldehyde, alkyne, and amine（A3） in 1,4-dioxane. The resuits show that the catalysts all displayed high reactivities, and a selectivity of 100% for propargylamines. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF have proved to be applicable to a wide range of substrates. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF can be easily recycled and used repetitively at least 3 times with a slight drop in activity. These features render the catalysts particularly attractive in the practice of propargylamines synthesis in an environmentally friendly manner.
Engineering metal-organic frameworks（MOF） for heterogeneous catalysts have been of extreme interest since they have large pore size within the crystalline framework and well defined pore architecture. Ni-containing MOF Ni2（3,5-Pydc）2（H2O）8·2H2O（1·H2O） was prepared by solvothermal method from 3,5-pyridinedicarboxylic acid, D-camphoric acid and Ni（NO3）2·6H2O in dimethylformamide（DMF）/water（volume ratio 2：1）. And two gold and silver functionalized 1·H2O catalysts were prepared by impregnation method. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF were in-depth characterized by single crystal X-ray diffraction, powder X-ray diffraction（PXRD）, thermogravimetric analysis（TGA）, transmission electron microscopy（TEM）, and inductively coupled plasma-atomic emission spectroscopy（ICP-AES）. Their catalytic performance was examined in one-pot synthesis of structurally divergent propargylamines via three component coupling of aldehyde, alkyne, and amine（A3） in 1,4-dioxane. The resuits show that the catalysts all displayed high reactivities, and a selectivity of 100% for propargylamines. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF have proved to be applicable to a wide range of substrates. Catalysts 2.53%Au/MOF and 4.23%Ag/MOF can be easily recycled and used repetitively at least 3 times with a slight drop in activity. These features render the catalysts particularly attractive in the practice of propargylamines synthesis in an environmentally friendly manner.
基金
Supported by the Promotive Research Fund for Young and Middle-aged Scientists of Shandong Province, China （Nos.BS2014CL021, BS2015CL012）, the Natural Science Foundation of Shandong Province, China（Nos.ZR2014BL003, ZR2015BM005）, the Project of Shandong Province Higher Educational Science and Technology Program, China（Nos.J14LC01, J 15LA09） and the Technology Research and Development Program of Weifang, China（No.201301035）.
