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Effect of Amine Modification on Catalytic Activity of ZIF-8 in Knoevenagel Condensation Reaction
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    Abstract:

    In this paper, different kinds of organic amines were used to modify ZIF-8 catalysts prepared via solvothermal method,and the effects of organic amine structural characteristics on the catalytic activity of ZIF-8 for Knoevenagel condensation reaction were discussed. The results show that ZIF-8 modified by organic amine still maintains the rhombohedral dodecahedron structure and possesses regular morphology,without obvious difference from that of unmodified materials. The BET specific surface areas of ZIF-8 modified by 1,2-propylenediamine,diethylenetriamine and triethylenetetramine are 1 893 m2·g-1,1 885 m2·g-1 and 1 861 m2·g-1,respectively, decreased by about 6.5% compared with that of the unmodified materials, mainly due to the blockage of pores for ZIF-8 by organic amines. When ethanol works as solvent, the amount of catalyst is 0.6 mol%(molar ratio to benzaldehyde),the reaction temperature is 80 ℃. When the reaction time keeps for 210 min,1,2-propanediamine modified ZIF-8 exhibits the highest catalyst activity,and the yield of ethyl α-cyanocinnamate reaches 97.8 %. After 10 cycles,the yield of this reaction is still up to 90 %,an increase of 35.3 % higher than that of unmodified ZIF-8. The studies on the catalytic mechanism of amine-modified ZIF-8 indicate that amines modified ZIF-8 can improve the amount of activity site,while 1,2-propanediamine has a shorter chain and less steric hindrance, making its N sites easier contact with reactants. It combines with the original imidazole N site on ZIF-8 to coordinate with α-H on the methylene of benzaldehyde through lone pair electrons, therefore significantly improving the catalytic activity of the catalyst clearly.

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  • Online: August 28,2020
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