Probing the Lewis acidity and catalytic activity of the metal-organic framework [Cu3(btc)2] (BTC = benzene-1,3,5-tricarboxylate)
Probing the Lewis acidity and catalytic activity of the metal-organic framework [Cu3(btc)2] (BTC = benzene-1,3,5-tricarboxylate)
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DOI：
10.1002/chem.200600220
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发表时间：
2006-09-25
影响因子：
4.3
通讯作者：
De Vos, Dirk E.
中科院分区：
文献类型：
--
作者：
Alaerts, Luc;Seguin, Etienne;De Vos, Dirk E.
设计了一种制备微孔金属有机骨架（MOF） [Cu-3(btc),] （btc =苯-1,3,5-三羧酸盐）的优化工艺。通过x射线衍射、光学显微镜、扫描电镜、x射线光电子能谱、N-2吸附、热重和红外光谱等手段对所吸附的CO进行了表征。CO吸附在少量的Cu2O杂质上，特别是在骨架中的游离Cu-II配位上。[Cu-3(btC)(2)]是萜类衍生物异构化的高选择性路易斯酸催化剂，如a-蒎烯氧化物重排为樟脑醛和香樟醛环化为异戊二醇。以2-溴丙烯酮的乙烯醛为底物，证实了[Cu-3(btC)(2)]的活性位点为硬路易斯酸。对催化剂的稳定性、可重用性和异质性进行了严格评估。
An optimized procedure was designed for the preparation of the microporous metal-organic framework (MOF) [Cu-3(btc),] (BTC=benzene-1,3,5-tricarboxylate). The crystalline material was characterized by X-ray diffraction, optical microscopy, SEM, X-ray photoelectron spectroscopy, N-2 sorption, thermogravimetry, and IR spectroscopy of adsorbed CO. CO adsorbs on a small number Of Cu2O impurities, and particularly on the free Cu-II coordination sites in the framework. [Cu-3(btC)(2)] is a highly selective Lewis acid catalyst for the isomerization of terpene derivatives, such as the rearrangement of a-pinene oxide to campholenic aldehyde and the cyclization of citronellal to isopulegol. By using the ethylene ketal of 2-bromopropiophenone as a test substrate, it was demonstrated that the active sites in [Cu-3(btC)(2)] are hard Lewis acids. Catalyst stability, re-usability, and heterogeneity are critically assessed.