Abstract
Trivalent cation (Co3+, Al3+, Er3+) containing-kenyaite and magadiite
lamellar silicates were synthesized and tested as catalysts for the
Knoevenagel condensation of butyraldehyde (BUT) with ethyl cyanoacetate
(CAE). The as-synthesized catalysts were thoroughly characterized by
X-ray powder diffraction (XRD), transmission electron microscopy (TEM),
Raman spectroscopy, solid state nuclear magnetic resonance of silicon
(Si-29 NMR) and nitrogen physisorption measurements. Significant effects
of the structural and textural features of kenyaite and magadiite on
catalyst activity in the Knoevenagel condensation were observed. The
high catalytic activity and selectivity were ascribed to the cations
incorporated into silicate layers, being Co3+ and Al3+ leached from
their structures during the reaction. Er3+-containing kenyaite exhibited
excellent catalytic activity in the Knoevenagel condensation, suggesting
that the presence of silanol groups along with trivalent cation was
responsible for the exceptional activity of the catalyst at mild
conditions. The effects of catalyst loading, type of solvent and
temperature on the catalytic properties demonstrated that a 100 mg of
catalyst mass and BUT/CAE molar ratio of 1 in the presence of toluene at
90 degrees C were the best conditions for testing Er3+-containing
kenyaite and magadiite catalysts. The affinity between Si and Er took
place in kenyaite structure and this could explain the better
performance of Er3+-containing kenyaite, since Er remained in the
framework during the reaction. On the contrary, leaching of the erbium
in magadiite was responsible for the lesser performance of the solid.
(C) 2014 Elsevier B.V. All rights reserved.
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