TY - JOUR
T1 - Rearrangement of α-pinene oxide to campholenic aldehyde over the trimesate metal-organic frameworks MIL-100, MIL-110 and MIL-96
AU - Timofeeva, Maria N.
AU - Panchenko, Valentina N.
AU - Abel, Anna A.
AU - Khan, Nazmul Abedin
AU - Ahmed, Imteaz
AU - Ayupov, Artem B.
AU - Volcho, Konstantin P.
AU - Jhung, Sung Hwa
PY - 2014/3
Y1 - 2014/3
N2 - The catalytic performance of porous metal-benzenetricarboxylates, such as MIL-100(Al, Fe and Cr), MIL-110(Al) and MIL-96(Al), was investigated with a combination of physicochemical and catalytic approaches in the rearrangement of α-pinene oxide to campholenic aldehyde (CA). The investigation of Lewis acidity was done by EPR and IR spectroscopy using 2,2′,6,6′- tetramethyl-1-piperidinyoxyl radical and benzonitrile as the probe molecules, respectively. For Al-BTCs, both these methods showed a decrease in the amount of Lewis acid sites as follows: MIL-100 > MIL-110 > MIL-96. The reaction rate and selectivity toward CA also decreased in the same order. A relatively good correlation between selectivity toward CA and the electronegativity of the metal ion was found for isostructural MIL-100(Al, Fe and Cr). The selectivity toward CA decreased in the order: MIL-100(Al) > MIL-100(Fe) > MIL-100(Cr). The high selectivity toward CA in the presence of MIL-100 has been suggested to originate from the unique structure of this material, which favors shape selectivity.
AB - The catalytic performance of porous metal-benzenetricarboxylates, such as MIL-100(Al, Fe and Cr), MIL-110(Al) and MIL-96(Al), was investigated with a combination of physicochemical and catalytic approaches in the rearrangement of α-pinene oxide to campholenic aldehyde (CA). The investigation of Lewis acidity was done by EPR and IR spectroscopy using 2,2′,6,6′- tetramethyl-1-piperidinyoxyl radical and benzonitrile as the probe molecules, respectively. For Al-BTCs, both these methods showed a decrease in the amount of Lewis acid sites as follows: MIL-100 > MIL-110 > MIL-96. The reaction rate and selectivity toward CA also decreased in the same order. A relatively good correlation between selectivity toward CA and the electronegativity of the metal ion was found for isostructural MIL-100(Al, Fe and Cr). The selectivity toward CA decreased in the order: MIL-100(Al) > MIL-100(Fe) > MIL-100(Cr). The high selectivity toward CA in the presence of MIL-100 has been suggested to originate from the unique structure of this material, which favors shape selectivity.
KW - Campholenic aldehyde
KW - Isomerization of α-pinene oxide
KW - Lewis acidity
KW - Metal-organic framework
UR - http://www.scopus.com/inward/record.url?scp=84890828716&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2013.11.006
DO - 10.1016/j.jcat.2013.11.006
M3 - Article
AN - SCOPUS:84890828716
SN - 0021-9517
VL - 311
SP - 114
EP - 120
JO - Journal of Catalysis
JF - Journal of Catalysis
ER -