Hydrogenation of nitro-compounds over rhodium catalysts supported on poly[acrylic acid]/Al2O3 composites

Cristian H. Campos, Edward Rosenberg, José L.G. Fierro, Bruno F. Urbano, Bernabé L. Rivas, Cecilia C. Torres, Patricio Reyes

Resultado de la investigación: Article

16 Citas (Scopus)

Resumen

In this report, poly[acrylic acid] gels containing Al2O3 were prepared by simultaneous free-radical polymerization and sol-gel chemistry using different amounts of 3-(trimethoxysilyl)propyl methacrylate (TMPM) as a compatibilizer. The hybrid materials were used as supports for a rhodium catalyst in the chemoselective hydrogenation of 3-substituted aromatic nitro-compounds. The supported rhodium catalyst was prepared by an ion-exchange process. In situ H2 flux was used to produce active species of the catalysts. The resulting materials were characterized by infrared spectroscopy, thermogravimetric analysis, solid-state 29Si and13 C NMR, X-ray diffraction, transmission/scanning electron microscopy, and X-ray photoelectron spectroscopy. All materials exhibited simultaneous interpenetrating hybrid network structures (SIHNs). The morphologies and physicochemical properties depended on the amount of TMPM used. The catalysts were found to be effective for the reduction of nitrobenzene in ethanol at room temperature and a hydrogen pressure of 20atm. The most active and selective catalyst was used in the hydrogenation of different 3-substituted aromatic nitro-compounds. The hydrogenation reactions displayed high conversion levels and promoted exclusive-NO2 group reduction, resulting in the sole formation of the corresponding amino-compound, with the exception of 1,3-dinitrobenzene, in which over-hydrogenation was detected. The presence of electron-donating/electron-withdrawing substituents at the 3-position resulted in different rates of-NO2group hydrogenation. This effect was quantified in terms of the Hammett relationship, in which the catalyst displayed a linear correlation between the substituent constant (σi) and the hydrogenation rate, with the exception of-OH, -NH2, and-OCH3 groups. One explanation for this behavior is a proposed support-substrate hydrogen bond interaction during the catalytic reaction.

Idioma originalEnglish
Páginas (desde-hasta)280-291
Número de páginas12
PublicaciónApplied Catalysis A: General
Volumen489
N.º1
DOI
EstadoPublished - 1 ene 2015

Huella dactilar

carbopol 940
Nitro Compounds
Rhodium
Catalyst supports
Acrylics
Hydrogenation
Catalysts
Acids
Composite materials
Nitrobenzene
Electrons
Compatibilizers
Hybrid materials
Free radical polymerization
Sol-gels
Thermogravimetric analysis
Hydrogen
Infrared spectroscopy
Ion exchange
Hydrogen bonds

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

Citar esto

Campos, Cristian H. ; Rosenberg, Edward ; Fierro, José L.G. ; Urbano, Bruno F. ; Rivas, Bernabé L. ; Torres, Cecilia C. ; Reyes, Patricio. / Hydrogenation of nitro-compounds over rhodium catalysts supported on poly[acrylic acid]/Al2O3 composites. En: Applied Catalysis A: General. 2015 ; Vol. 489, N.º 1. pp. 280-291.
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title = "Hydrogenation of nitro-compounds over rhodium catalysts supported on poly[acrylic acid]/Al2O3 composites",
abstract = "In this report, poly[acrylic acid] gels containing Al2O3 were prepared by simultaneous free-radical polymerization and sol-gel chemistry using different amounts of 3-(trimethoxysilyl)propyl methacrylate (TMPM) as a compatibilizer. The hybrid materials were used as supports for a rhodium catalyst in the chemoselective hydrogenation of 3-substituted aromatic nitro-compounds. The supported rhodium catalyst was prepared by an ion-exchange process. In situ H2 flux was used to produce active species of the catalysts. The resulting materials were characterized by infrared spectroscopy, thermogravimetric analysis, solid-state 29Si and13 C NMR, X-ray diffraction, transmission/scanning electron microscopy, and X-ray photoelectron spectroscopy. All materials exhibited simultaneous interpenetrating hybrid network structures (SIHNs). The morphologies and physicochemical properties depended on the amount of TMPM used. The catalysts were found to be effective for the reduction of nitrobenzene in ethanol at room temperature and a hydrogen pressure of 20atm. The most active and selective catalyst was used in the hydrogenation of different 3-substituted aromatic nitro-compounds. The hydrogenation reactions displayed high conversion levels and promoted exclusive-NO2 group reduction, resulting in the sole formation of the corresponding amino-compound, with the exception of 1,3-dinitrobenzene, in which over-hydrogenation was detected. The presence of electron-donating/electron-withdrawing substituents at the 3-position resulted in different rates of-NO2group hydrogenation. This effect was quantified in terms of the Hammett relationship, in which the catalyst displayed a linear correlation between the substituent constant (σi) and the hydrogenation rate, with the exception of-OH, -NH2, and-OCH3 groups. One explanation for this behavior is a proposed support-substrate hydrogen bond interaction during the catalytic reaction.",
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Hydrogenation of nitro-compounds over rhodium catalysts supported on poly[acrylic acid]/Al2O3 composites. / Campos, Cristian H.; Rosenberg, Edward; Fierro, José L.G.; Urbano, Bruno F.; Rivas, Bernabé L.; Torres, Cecilia C.; Reyes, Patricio.

En: Applied Catalysis A: General, Vol. 489, N.º 1, 01.01.2015, p. 280-291.

Resultado de la investigación: Article

TY - JOUR

T1 - Hydrogenation of nitro-compounds over rhodium catalysts supported on poly[acrylic acid]/Al2O3 composites

AU - Campos, Cristian H.

AU - Rosenberg, Edward

AU - Fierro, José L.G.

AU - Urbano, Bruno F.

AU - Rivas, Bernabé L.

AU - Torres, Cecilia C.

AU - Reyes, Patricio

PY - 2015/1/1

Y1 - 2015/1/1

N2 - In this report, poly[acrylic acid] gels containing Al2O3 were prepared by simultaneous free-radical polymerization and sol-gel chemistry using different amounts of 3-(trimethoxysilyl)propyl methacrylate (TMPM) as a compatibilizer. The hybrid materials were used as supports for a rhodium catalyst in the chemoselective hydrogenation of 3-substituted aromatic nitro-compounds. The supported rhodium catalyst was prepared by an ion-exchange process. In situ H2 flux was used to produce active species of the catalysts. The resulting materials were characterized by infrared spectroscopy, thermogravimetric analysis, solid-state 29Si and13 C NMR, X-ray diffraction, transmission/scanning electron microscopy, and X-ray photoelectron spectroscopy. All materials exhibited simultaneous interpenetrating hybrid network structures (SIHNs). The morphologies and physicochemical properties depended on the amount of TMPM used. The catalysts were found to be effective for the reduction of nitrobenzene in ethanol at room temperature and a hydrogen pressure of 20atm. The most active and selective catalyst was used in the hydrogenation of different 3-substituted aromatic nitro-compounds. The hydrogenation reactions displayed high conversion levels and promoted exclusive-NO2 group reduction, resulting in the sole formation of the corresponding amino-compound, with the exception of 1,3-dinitrobenzene, in which over-hydrogenation was detected. The presence of electron-donating/electron-withdrawing substituents at the 3-position resulted in different rates of-NO2group hydrogenation. This effect was quantified in terms of the Hammett relationship, in which the catalyst displayed a linear correlation between the substituent constant (σi) and the hydrogenation rate, with the exception of-OH, -NH2, and-OCH3 groups. One explanation for this behavior is a proposed support-substrate hydrogen bond interaction during the catalytic reaction.

AB - In this report, poly[acrylic acid] gels containing Al2O3 were prepared by simultaneous free-radical polymerization and sol-gel chemistry using different amounts of 3-(trimethoxysilyl)propyl methacrylate (TMPM) as a compatibilizer. The hybrid materials were used as supports for a rhodium catalyst in the chemoselective hydrogenation of 3-substituted aromatic nitro-compounds. The supported rhodium catalyst was prepared by an ion-exchange process. In situ H2 flux was used to produce active species of the catalysts. The resulting materials were characterized by infrared spectroscopy, thermogravimetric analysis, solid-state 29Si and13 C NMR, X-ray diffraction, transmission/scanning electron microscopy, and X-ray photoelectron spectroscopy. All materials exhibited simultaneous interpenetrating hybrid network structures (SIHNs). The morphologies and physicochemical properties depended on the amount of TMPM used. The catalysts were found to be effective for the reduction of nitrobenzene in ethanol at room temperature and a hydrogen pressure of 20atm. The most active and selective catalyst was used in the hydrogenation of different 3-substituted aromatic nitro-compounds. The hydrogenation reactions displayed high conversion levels and promoted exclusive-NO2 group reduction, resulting in the sole formation of the corresponding amino-compound, with the exception of 1,3-dinitrobenzene, in which over-hydrogenation was detected. The presence of electron-donating/electron-withdrawing substituents at the 3-position resulted in different rates of-NO2group hydrogenation. This effect was quantified in terms of the Hammett relationship, in which the catalyst displayed a linear correlation between the substituent constant (σi) and the hydrogenation rate, with the exception of-OH, -NH2, and-OCH3 groups. One explanation for this behavior is a proposed support-substrate hydrogen bond interaction during the catalytic reaction.

KW - Hybrid materials

KW - Hydrogenation

KW - Metallic catalysts

KW - Rhodium

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U2 - 10.1016/j.apcata.2014.10.029

DO - 10.1016/j.apcata.2014.10.029

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