Amino-functionalized basic catalysts with MIL-101 structure
Amino-functionalized basic catalysts with MIL-101 structure
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DOI：
10.1016/j.micromeso.2012.06.044
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发表时间：
2012-12-01
影响因子：
5.2
通讯作者：
Fischer, Marcus
中科院分区：
文献类型：
--
作者：
Hartmann, Martin;Fischer, Marcus
金属有机骨架（MOF）材料在多相催化领域的应用研究是近几年才开始的。除了使用MOF作为高度分散的金属颗粒的沉积的支持，活性中心，如配位不饱和的金属网站和功能化的有机连接器与酸性或碱性基团的掺入似乎是最有前途的。在我们的贡献中，三种不同的MOFs在其有机接头处携带氨基，即Fe-MIL-101-NH 2（S-BET = 3438 m（2）g（-1）），Al-MIL-101-NH2（S-BET = 3099 m（2）g（-1））和CAU-1（S-BET = 1492 m（2）g（-1）），并分别在苯甲醛与丙二腈和与氰乙酸乙酯的Knoevenagel缩合反应中进行了测试。结果表明，在3小时后，形成了预期产物亚苄基丙二腈（BzMN）和α-氰基肉桂酸乙酯（EtCC），选择性超过99%，产率为90 - 95%（对于BzMN）。由于CAU-1的孔窗口非常小（0.3至0.4 nm），与氨基-MIL-101衍生物相比，反应在该催化剂上进行得慢得多，氨基-MIL-101衍生物具有高达1.6 nm的开孔窗口。此外，催化剂Al-MIL-101-NH 2是可再循环的，而没有显著的活性损失。(C)2012 Elsevier Inc. All rights reserved.
Metal-organic framework (MOF) materials have only been scarcely explored for applications in heterogeneous catalysis in recent years. In addition to the use of MOFs as supports for the deposition of highly dispersed metal particles, the incorporation of active centers such as coordinatively unsaturated metal sites and the functionalization of the organic linkers with acidic or basic groups seem to be most promising. In our contribution, three different MOFs carrying amino groups at their organic linkers, namely Fe-MIL-101-NH2 (S-BET = 3438 m(2) g(-1)), Al-MIL-101-NH2 (S-BET = 3099 m(2) g(-1)) and CAU-1 (S-BET = 1492 m(2) g(-1)), were synthesized and tested in the Knoevenagel condensation of benzaldehyde with malononitrile and with ethyl cyanoacetate, respectively. It is shown that the expected products benzylidenemalononitrile (BzMN) and ethyl alpha-cyanocinnamate (EtCC) are formed with selectivities exceeding 99% and yields of 90 to 95% after 3 h (for BzMN). Due to the very small pore windows of CAU-1 (0.3 to 0.4 nm) the reaction proceeds much slower over this catalyst in comparison to the amino-MIL-101 derivatives, which possess open pore windows of up to 1.6 nm. Moreover, the catalyst Al-MIL-101-NH2 is recyclable without significant loss of activity. (C) 2012 Elsevier Inc. All rights reserved.