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Probing the Lewis Acidity and Catalytic Activity of the Metal–Organic Framework [Cu 3 (btc) 2 ] (BTC=Benzene‐1,3,5‐tricarboxylate)
Author(s) -
Alaerts Luc,
Séguin Etienne,
Poelman Hilde,
ThibaultStarzyk Frédéric,
Jacobs Pierre A.,
De Vos Dirk E.
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600220
Subject(s) - metal organic framework , catalysis , lewis acids and bases , chemistry , benzene , microporous material , heterogeneous catalysis , inorganic chemistry , adsorption , organic chemistry
An optimized procedure was designed for the preparation of the microporous metal–organic framework (MOF) [Cu 3 (btc) 2 ] (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 Cu 2 O 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 α‐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.