TY - JOUR
T1 - Catalytic behavior of metal-organic frameworks in the Knoevenagel condensation reaction
AU - Panchenko, Valentina N.
AU - Matrosova, Maria M.
AU - Jeon, Jaewoo
AU - Jun, Jong Won
AU - Timofeeva, Maria N.
AU - Jhung, Sung Hwa
PY - 2014/7
Y1 - 2014/7
N2 - Effect of basicity of porous metal-carboxylates, such as MIL-100(Al), Cu3(BTC)2·(H2O)3, UiO-66 and amino-modified UiO-66 materials (UiO-66-NH2) on their catalytic performance, was studied in the Knoevenagel condensation of benzaldehyde with malononitrile to 2-benzylidenemalononitrile. According to physicochemical studies, the strength of the basic sites for MIL-100(Al), Cu3(BTC) 2·(H2O)3, UiO-66 was in the range of 830-839 kJ/mol, while the amount of basic sites decreased in the order MIL-100(Al) > Cu3(BTC)2·(H2O) 3 > UiO-66. The insertion of NH2 groups into the UiO-66 framework led to an increase in the strength of basic sites from 839 to 867 kJ/mol. The catalytic activity of metal carboxylates correlated with the amount of basic sites and the strength of the interaction between metal and oxygen in the "M+n-O2- Lewis acid-base" pair, which was estimated from ionic covalent parameters. The activity of the UiO-66-NH 2 materials was higher than that of UiO-66.
AB - Effect of basicity of porous metal-carboxylates, such as MIL-100(Al), Cu3(BTC)2·(H2O)3, UiO-66 and amino-modified UiO-66 materials (UiO-66-NH2) on their catalytic performance, was studied in the Knoevenagel condensation of benzaldehyde with malononitrile to 2-benzylidenemalononitrile. According to physicochemical studies, the strength of the basic sites for MIL-100(Al), Cu3(BTC) 2·(H2O)3, UiO-66 was in the range of 830-839 kJ/mol, while the amount of basic sites decreased in the order MIL-100(Al) > Cu3(BTC)2·(H2O) 3 > UiO-66. The insertion of NH2 groups into the UiO-66 framework led to an increase in the strength of basic sites from 839 to 867 kJ/mol. The catalytic activity of metal carboxylates correlated with the amount of basic sites and the strength of the interaction between metal and oxygen in the "M+n-O2- Lewis acid-base" pair, which was estimated from ionic covalent parameters. The activity of the UiO-66-NH 2 materials was higher than that of UiO-66.
KW - Amino-modified UiO-66
KW - Basic properties
KW - Catalytic properties
KW - Knoevenagel condensation
KW - Metal-organic frameworks
UR - http://www.scopus.com/inward/record.url?scp=84903541241&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2014.05.018
DO - 10.1016/j.jcat.2014.05.018
M3 - Article
AN - SCOPUS:84903541241
SN - 0021-9517
VL - 316
SP - 251
EP - 259
JO - Journal of Catalysis
JF - Journal of Catalysis
ER -