Catalytic behavior of metal-organic frameworks in the Knoevenagel condensation reaction

Valentina N. Panchenko; Maria M. Matrosova; Jaewoo Jeon; Jong Won Jun; Maria N. Timofeeva; Sung Hwa Jhung

doi:10.1016/j.jcat.2014.05.018

Catalytic behavior of metal-organic frameworks in the Knoevenagel condensation reaction

Valentina N. Panchenko
, Maria M. Matrosova
, Jaewoo Jeon
, Jong Won Jun
, Maria N. Timofeeva
, Sung Hwa Jhung

RAS - Boreskov Institute of Catalysis, Siberian Branch
Kyungpook National University
Novosibirsk State Technical University

Research output: Contribution to journal › Article › peer-review

141 Scopus citations

Abstract

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-O^2- 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.

Original language	English
Pages (from-to)	251-259
Number of pages	9
Journal	Journal of Catalysis
Volume	316
DOIs	https://doi.org/10.1016/j.jcat.2014.05.018
State	Published - Jul 2014

Keywords

Amino-modified UiO-66
Basic properties
Catalytic properties
Knoevenagel condensation
Metal-organic frameworks

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10.1016/j.jcat.2014.05.018

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@article{0308adc94696432c9952b0040046f150,

title = "Catalytic behavior of metal-organic frameworks in the Knoevenagel condensation reaction",

abstract = "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.",

keywords = "Amino-modified UiO-66, Basic properties, Catalytic properties, Knoevenagel condensation, Metal-organic frameworks",

author = "Panchenko, \{Valentina N.\} and Matrosova, \{Maria M.\} and Jaewoo Jeon and Jun, \{Jong Won\} and Timofeeva, \{Maria N.\} and Jhung, \{Sung Hwa\}",

year = "2014",

month = jul,

doi = "10.1016/j.jcat.2014.05.018",

language = "English",

volume = "316",

pages = "251--259",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

}

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 - https://www.scopus.com/pages/publications/84903541241

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 -

Catalytic behavior of metal-organic frameworks in the Knoevenagel condensation reaction

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Keywords

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