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有机胺改性对ZIF-8催化Knoevenagel缩合反应活性的影响
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湖南大学材料科学与工程学院

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Effect of amine modification on the catalytic activity of ZIF-8 in Knoevenagel condensation
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College of Materials Science and Engineering,Hunan University

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    摘要:

    采用不同结构的有机胺改性溶剂热法合成的ZIF-8催化剂,探讨了胺结构特性对ZIF-8催化Knoevenagel缩合反应活性的影响。结果表明,有机胺改性后ZIF-8保持菱形十二面体结构,形貌规则,与未改性材料无明显差别,1, 2丙二胺,二乙烯三胺和三乙烯四胺改性ZIF-8后的BET比表面积分别为1893、1885和1861 m2?g-1,较之改性前下降约6.5%,这主要是由于接枝在ZIF-8表面的有机胺堵塞了其孔道;采用乙醇作溶剂,催化剂添加量为0.6mol%,反应温度80oC,210 min时,1, 2丙二胺改性ZIF-8对K反应的催化活性最高,α-氰基肉桂酸乙酯的产率达97.8%,循环10次后,产率依旧保持90%以上,较未改性催化剂产率提高35.3%。对胺改性ZIF-8的催化机理研究表明:有机胺改性ZIF-8可增加其催化活性位点,而1, 2丙二胺因链短,空间位阻小,其N活性位点更易与反应物接触,与ZIF-8上原有的咪唑N位点一起通过孤对电子与反应物苯甲醛的亚甲基上的?-H配位,从而显著提高催化剂的活性。

    Abstract:

    In this paper, different kinds of organic amines are used to modify ZIF-8 catalysts prepared via solvothermal method, and effects of organic amine structural characteristics on the activity of ZIF-8 for Knoevenagel condensation were discussed. 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 1893, 1885 and 1861 m2?g-1, respectively, decreased by about 6.5% compared with the unmodified materials, mainly being 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%, the reaction temperature is at 80oC and reaction time keeps for 210 min, 1, 2-propanediamine modified ZIF-8 exhibits the highest catalyst activity, yield of ethyl α-cyanocinnamate reaches 97.8%. After 10 cycles, yield of this reaction is still up to 90%, 35.3% higher than that of unmodified ZIF-8. Amines modified ZIF-8 can improve the amount of activity site, in which, N sites existed in 1, 2-propanediamine are easier to meet with the reactant due to the short chain and small steric hindrance, which combines with the original imidazole N site on ZIF-8 to coordinate with α-H on the methylene of benzaldehyde through lone pair electrons, so as to improve the catalytic activity of the catalyst clearly.

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历史
  • 收稿日期: 2019-11-20
  • 最后修改日期: 2019-12-31
  • 录用日期: 2020-01-07
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