高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (8): 1655-1661.doi: 10.7503/cjcu20190201

• 物理化学 • 上一篇    下一篇

MIL-53系列金属有机骨架化合物的合成及在Strecker反应中的催化性能

王鹏程1, 单梁2, 范勇1, 王莉1, 徐家宁1, 吴淑杰1   

  1. 1. 吉林大学化学学院, 长春 130012;
    2. 安阳工学院化学与环境工程学院, 安阳 455000
  • 收稿日期:2019-04-03 修回日期:2019-07-23 出版日期:2019-08-10 发布日期:2019-07-12
  • 通讯作者: 徐家宁,男,博士,教授,博士生导师,主要从事功能无机化合物合成方面的研究.E-mail:xujn@jlu.edu.cn E-mail:xujn@jlu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号:21171065,51775232,21401005)资助.

Syntheses of MIL-53 MOFs Materials and Their Catalytic Properties in Strecker Reactions

WANG Pengcheng1, SHAN Liang2, FAN Yong1, WANG Li1, XU Jianing1, WU Shujie1   

  1. 1. College of Chemistry, Jilin University, Changchun 130012, China;
    2. College of Chemistry and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, China
  • Received:2019-04-03 Revised:2019-07-23 Online:2019-08-10 Published:2019-07-12
  • Supported by:
    Supported by the National Natural Science Foundation of China(Nos.21171065, 51775232, 21401005).

摘要: 通过改变金属中心和配体官能团,合成了4个MIL-53系列金属有机骨架化合物NH2-MIL-53(Sc),NH2-MIL-53(Al),MIL-53(Sc)和NO2-MIL-53(Sc);研究了它们在合成α-氨基腈的Strecker反应中的催化性能.结果表明,NH2-MIL-53(Sc)对于Strecker反应具有优异的催化性能,并具有可重复使用性.通过对比NH2-MIL-53(Sc)和NH2-MIL-53(Al)的催化性能,分析了金属离子半径和金属中心不饱和配位点对Strecker反应的影响.通过对比NH2-MIL-53(Sc)与MIL-53(Sc)的催化性能,证明了作为路易斯碱中心的氨基可通过与路易斯酸中心的协同作用,有效促进Strecker反应的进行.通过对比NO2-MIL-53(Sc)与MIL-53(Sc)的催化性能,认为催化剂结构上的硝基对于Strecker反应的进行具有重要影响.最后,通过对比NH2-MIL-53(Sc)、硝酸钪和2-氨基对苯二甲酸(ATA)配体对催化性能的影响,总结出催化剂在纳米尺度的孔道结构是提高Strecker反应选择性的关键因素.

关键词: 金属有机骨架, MIL-53, 路易斯酸/碱双功能催化, 孔道结构, Strecker反应

Abstract: Four metal organic frameworks(MOFs), NH2-MIL-53(Sc), NH2-MIL-53(Al), MIL-53(Sc) and NO2-MIL-53(Sc), were synthesized via changing the metal center and functional group of ligand, hereafter, their catalytic performance in the formation of α-aminonitrile(donated Strecker reaction) was investigated. Noteworthy, it is shown that the reusable NH2-MIL-53(Sc) shows very good catalytic performance for Strecker reaction. Hereafter, comparing the catalytic experiments between NH2-MIL-53(Sc) and NH2-MIL-53(Al), the influence of metal ion radius and unsaturated coordination metal sites on Strecker reaction were analyzed. Furthermore, in comparison with the catalytic effects between NH2-MIL-53(Sc) and MIL-53(Sc), the results demonstrated that the amino group can be served as the Lewis base sites, which can promote Strecker reaction through Lewis acid and Lewis base bifunctional synergistic mechanism. In addition, comparing the catalytic performances between NO2-MIL-53(Sc) and MIL-53(Sc), it is confirmed that the NO2 group on the catalyst structure has an important influence on the Strecker reaction. Finally, in comparison with the catalytic effects among NH2-MIL-53(Sc), scandium nitrate and 2-aminoterephthalic acid(ATA) ligand, it is concluded that the nanoscale pore structure of NH2-MIL-53(Sc) is the key factor to improve the selectivity of product in Strecker reaction.

Key words: Metal organic frameworks, MIL-53, Lewis acid and Lewis base bifunctional catalysis, Porous structure, Strecker reaction

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