TY - JOUR
T1 - Effect of the support on the basic and catalytic properties of KF
AU - Clacens, Jean Marc
AU - Genuit, Daisy
AU - Delmotte, Luc
AU - Garcia-Ruiz, Amado
AU - Bergeret, Gérard
AU - Montiel, Ramon
AU - Lopez, Joseph
AU - Figueras, François
N1 - Funding Information:
The work of the analytical service of IRC for the analysis of the solids is warmly acknowledged. A.G.R. thanks CONACYT and COFAA-IPN, Mexico, for the financial support of his stay at IRC.
PY - 2004/1/25
Y1 - 2004/1/25
N2 - KF supported by various supports was characterized by DTG-DTA coupled with mass spectral analysis of the gases evolved by the solid, in situ XRD, calorimetry, 19F NMR spectroscopy, and tested in the Michael addition of cyclohexene-2-one with nitroalkanes. After dehydration at low temperatures, from 19F NMR spectroscopy F is in part as KF when the support is α-alumina but only as K3AlF6 when the support is γ-alumina. During activation no fluorine is lost. On α-alumina KF is detected by XRD only after calcination at about 723 K and results in part of the decomposition of K3AlF6; it disappears with formation of K2AlF5 and KAlO2 at higher temperatures. A comparison of the results obtained by XRD and NMR suggests that KF is well dispersed on α-alumina. KF/α-alumina is a strong base, stronger than KF on γ-alumina, and more active for Michael reactions. On KF/α-alumina the Michael condensation of 2-cyclohexen-1-one with nitroalkanes can be achieved in 5 min with an equimolar mixture of reactants. Solvent-free reactions can also be achieved reaching 75% yield in adduct after 8 h, and KF/α-alumina is also active after simple drying at 393 K, avoiding the usual activation at higher; temperatures.
AB - KF supported by various supports was characterized by DTG-DTA coupled with mass spectral analysis of the gases evolved by the solid, in situ XRD, calorimetry, 19F NMR spectroscopy, and tested in the Michael addition of cyclohexene-2-one with nitroalkanes. After dehydration at low temperatures, from 19F NMR spectroscopy F is in part as KF when the support is α-alumina but only as K3AlF6 when the support is γ-alumina. During activation no fluorine is lost. On α-alumina KF is detected by XRD only after calcination at about 723 K and results in part of the decomposition of K3AlF6; it disappears with formation of K2AlF5 and KAlO2 at higher temperatures. A comparison of the results obtained by XRD and NMR suggests that KF is well dispersed on α-alumina. KF/α-alumina is a strong base, stronger than KF on γ-alumina, and more active for Michael reactions. On KF/α-alumina the Michael condensation of 2-cyclohexen-1-one with nitroalkanes can be achieved in 5 min with an equimolar mixture of reactants. Solvent-free reactions can also be achieved reaching 75% yield in adduct after 8 h, and KF/α-alumina is also active after simple drying at 393 K, avoiding the usual activation at higher; temperatures.
KW - Activation of supported KF
KW - Basic strength
KW - Michael addition
KW - Solid base
KW - Solvent-free reactions
KW - Thermal analysis
KW - XRD
UR - http://www.scopus.com/inward/record.url?scp=0742290037&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2003.09.009
DO - 10.1016/j.jcat.2003.09.009
M3 - Artículo
SN - 0021-9517
VL - 221
SP - 483
EP - 490
JO - Journal of Catalysis
JF - Journal of Catalysis
IS - 2
ER -