Framework Breathing in the Vapour-Phase Adsorption and Separation of Xylene Isomers with the Metal-Organic Framework MIL-53

Vapour‐phase adsorption and separation of the C8 alkyl aromatic compounds p‐xylene, m‐xylene, o‐xylene, and ethylbenzene has been studied on the metal–organic framework MIL‐53. Adsorption and desorption isotherms of the pure components at 110 °C were determined using the gravimetric technique. The a...

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Vydané v:Chemistry : a European journal Ročník 15; číslo 31; s. 7724 - 7731
Hlavní autori: Finsy, Vincent, Kirschhock, Christine E. A., Vedts, Gill, Maes, Michael, Alaerts, Luc, De Vos, Dirk E., Baron, Gino V., Denayer, Joeri F. M.
Médium: Journal Article
Jazyk:English
Vydavateľské údaje: Weinheim WILEY-VCH Verlag 03.08.2009
WILEY‐VCH Verlag
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ISSN:0947-6539, 1521-3765, 1521-3765
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Abstract Vapour‐phase adsorption and separation of the C8 alkyl aromatic compounds p‐xylene, m‐xylene, o‐xylene, and ethylbenzene has been studied on the metal–organic framework MIL‐53. Adsorption and desorption isotherms of the pure components at 110 °C were determined using the gravimetric technique. The adsorption isotherms show two well‐defined steps and hysteresis, corresponding to the opening or breathing of the framework, as induced by the presence of the adsorbing molecules. In the first isotherm plateau, an adsorption capacity of about 18 wt % is observed. After the breathing phenomenon, the adsorption capacity increases to about 40 wt %. Breakthrough separation experiments with equimolar o‐xylene/ethylbenzene mixtures were performed at 110 °C with varying hydrocarbon pressures. The separation mechanism is related to the state of the pore structure, as dictated by framework breathing. At low pressure, below the “pore‐opening” pressure, MIL‐53 shows no preference for any isomer. At pressures high enough to induce pore opening, separation of the C8 alkyl aromatic isomers becomes possible and separation factors as high as 6.5 are observed. The separation at a high degree of pore filling in the open form is a result of differences in the packing modes of the C8 alkyl aromatic components in the pores of MIL‐53. Isomer separation on MIL‐53: Framework breathing permits separation of xylene isomers (see picture). At low pressures (top), adsorption of C8 alkyl aromatic compounds induces contraction of the MIL‐53 (Al) framework. Under these conditions, there is no difference in adsorption between the various isomers. No separation is possible. At higher pressures (bottom), the framework is reopened and additional molecules are adsorbed in a selective way.
AbstractList Vapour‐phase adsorption and separation of the C8 alkyl aromatic compounds p‐xylene, m‐xylene, o‐xylene, and ethylbenzene has been studied on the metal–organic framework MIL‐53. Adsorption and desorption isotherms of the pure components at 110 °C were determined using the gravimetric technique. The adsorption isotherms show two well‐defined steps and hysteresis, corresponding to the opening or breathing of the framework, as induced by the presence of the adsorbing molecules. In the first isotherm plateau, an adsorption capacity of about 18 wt % is observed. After the breathing phenomenon, the adsorption capacity increases to about 40 wt %. Breakthrough separation experiments with equimolar o‐xylene/ethylbenzene mixtures were performed at 110 °C with varying hydrocarbon pressures. The separation mechanism is related to the state of the pore structure, as dictated by framework breathing. At low pressure, below the “pore‐opening” pressure, MIL‐53 shows no preference for any isomer. At pressures high enough to induce pore opening, separation of the C8 alkyl aromatic isomers becomes possible and separation factors as high as 6.5 are observed. The separation at a high degree of pore filling in the open form is a result of differences in the packing modes of the C8 alkyl aromatic components in the pores of MIL‐53. Isomer separation on MIL‐53: Framework breathing permits separation of xylene isomers (see picture). At low pressures (top), adsorption of C8 alkyl aromatic compounds induces contraction of the MIL‐53 (Al) framework. Under these conditions, there is no difference in adsorption between the various isomers. No separation is possible. At higher pressures (bottom), the framework is reopened and additional molecules are adsorbed in a selective way.
Vapour‐phase adsorption and separation of the C8 alkyl aromatic compounds p ‐xylene, m ‐xylene, o ‐xylene, and ethylbenzene has been studied on the metal–organic framework MIL‐53. Adsorption and desorption isotherms of the pure components at 110 °C were determined using the gravimetric technique. The adsorption isotherms show two well‐defined steps and hysteresis, corresponding to the opening or breathing of the framework, as induced by the presence of the adsorbing molecules. In the first isotherm plateau, an adsorption capacity of about 18 wt % is observed. After the breathing phenomenon, the adsorption capacity increases to about 40 wt %. Breakthrough separation experiments with equimolar o ‐xylene/ethylbenzene mixtures were performed at 110 °C with varying hydrocarbon pressures. The separation mechanism is related to the state of the pore structure, as dictated by framework breathing. At low pressure, below the “pore‐opening” pressure, MIL‐53 shows no preference for any isomer. At pressures high enough to induce pore opening, separation of the C8 alkyl aromatic isomers becomes possible and separation factors as high as 6.5 are observed. The separation at a high degree of pore filling in the open form is a result of differences in the packing modes of the C8 alkyl aromatic components in the pores of MIL‐53.
Vapour-phase adsorption and separation of the C8 alkyl aromatic compounds p-xylene, m-xylene, o-xylene, and ethylbenzene has been studied on the metal-organic framework MIL-53. Adsorption and desorption isotherms of the pure components at 110 degrees C were determined using the gravimetric technique. The adsorption isotherms show two well-defined steps and hysteresis, corresponding to the opening or breathing of the framework, as induced by the presence of the adsorbing molecules. In the first isotherm plateau, an adsorption capacity of about 18 wt % is observed. After the breathing phenomenon, the adsorption capacity increases to about 40 wt %. Breakthrough separation experiments with equimolar o-xylene/ethylbenzene mixtures were performed at 110 degrees C with varying hydrocarbon pressures. The separation mechanism is related to the state of the pore structure, as dictated by framework breathing. At low pressure, below the "pore-opening" pressure, MIL-53 shows no preference for any isomer. At pressures high enough to induce pore opening, separation of the C8 alkyl aromatic isomers becomes possible and separation factors as high as 6.5 are observed. The separation at a high degree of pore filling in the open form is a result of differences in the packing modes of the C8 alkyl aromatic components in the pores of MIL-53.Vapour-phase adsorption and separation of the C8 alkyl aromatic compounds p-xylene, m-xylene, o-xylene, and ethylbenzene has been studied on the metal-organic framework MIL-53. Adsorption and desorption isotherms of the pure components at 110 degrees C were determined using the gravimetric technique. The adsorption isotherms show two well-defined steps and hysteresis, corresponding to the opening or breathing of the framework, as induced by the presence of the adsorbing molecules. In the first isotherm plateau, an adsorption capacity of about 18 wt % is observed. After the breathing phenomenon, the adsorption capacity increases to about 40 wt %. Breakthrough separation experiments with equimolar o-xylene/ethylbenzene mixtures were performed at 110 degrees C with varying hydrocarbon pressures. The separation mechanism is related to the state of the pore structure, as dictated by framework breathing. At low pressure, below the "pore-opening" pressure, MIL-53 shows no preference for any isomer. At pressures high enough to induce pore opening, separation of the C8 alkyl aromatic isomers becomes possible and separation factors as high as 6.5 are observed. The separation at a high degree of pore filling in the open form is a result of differences in the packing modes of the C8 alkyl aromatic components in the pores of MIL-53.
Vapour-phase adsorption and separation of the C8 alkyl aromatic compounds p-xylene, m-xylene, o-xylene, and ethylbenzene has been studied on the metal-organic framework MIL-53. Adsorption and desorption isotherms of the pure components at 110 degrees C were determined using the gravimetric technique. The adsorption isotherms show two well-defined steps and hysteresis, corresponding to the opening or breathing of the framework, as induced by the presence of the adsorbing molecules. In the first isotherm plateau, an adsorption capacity of about 18 wt % is observed. After the breathing phenomenon, the adsorption capacity increases to about 40 wt %. Breakthrough separation experiments with equimolar o-xylene/ethylbenzene mixtures were performed at 110 degrees C with varying hydrocarbon pressures. The separation mechanism is related to the state of the pore structure, as dictated by framework breathing. At low pressure, below the "pore-opening" pressure, MIL-53 shows no preference for any isomer. At pressures high enough to induce pore opening, separation of the C8 alkyl aromatic isomers becomes possible and separation factors as high as 6.5 are observed. The separation at a high degree of pore filling in the open form is a result of differences in the packing modes of the C8 alkyl aromatic components in the pores of MIL-53.
Author Vedts, Gill
Kirschhock, Christine E. A.
Denayer, Joeri F. M.
Finsy, Vincent
Maes, Michael
Baron, Gino V.
Alaerts, Luc
De Vos, Dirk E.
Author_xml – sequence: 1
  givenname: Vincent
  surname: Finsy
  fullname: Finsy, Vincent
  organization: Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussel (Belgium), Fax: (+32) 26293248
– sequence: 2
  givenname: Christine E. A.
  surname: Kirschhock
  fullname: Kirschhock, Christine E. A.
  organization: Centrum voor oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Leuven (Belgium)
– sequence: 3
  givenname: Gill
  surname: Vedts
  fullname: Vedts, Gill
  organization: Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussel (Belgium), Fax: (+32) 26293248
– sequence: 4
  givenname: Michael
  surname: Maes
  fullname: Maes, Michael
  organization: Centrum voor oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Leuven (Belgium)
– sequence: 5
  givenname: Luc
  surname: Alaerts
  fullname: Alaerts, Luc
  organization: Centrum voor oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Leuven (Belgium)
– sequence: 6
  givenname: Dirk E.
  surname: De Vos
  fullname: De Vos, Dirk E.
  organization: Centrum voor oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Leuven (Belgium)
– sequence: 7
  givenname: Gino V.
  surname: Baron
  fullname: Baron, Gino V.
  organization: Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussel (Belgium), Fax: (+32) 26293248
– sequence: 8
  givenname: Joeri F. M.
  surname: Denayer
  fullname: Denayer, Joeri F. M.
  email: joeri.denayer@vub.ac.be
  organization: Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussel (Belgium), Fax: (+32) 26293248
BackLink https://www.ncbi.nlm.nih.gov/pubmed/19551773$$D View this record in MEDLINE/PubMed
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Snippet Vapour‐phase adsorption and separation of the C8 alkyl aromatic compounds p‐xylene, m‐xylene, o‐xylene, and ethylbenzene has been studied on the metal–organic...
Vapour‐phase adsorption and separation of the C8 alkyl aromatic compounds p ‐xylene, m ‐xylene, o ‐xylene, and ethylbenzene has been studied on the...
Vapour-phase adsorption and separation of the C8 alkyl aromatic compounds p-xylene, m-xylene, o-xylene, and ethylbenzene has been studied on the metal-organic...
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SubjectTerms adsorption
framework breathing
metal-organic frameworks
xylene separation
Title Framework Breathing in the Vapour-Phase Adsorption and Separation of Xylene Isomers with the Metal-Organic Framework MIL-53
URI https://api.istex.fr/ark:/67375/WNG-1N4LBH70-0/fulltext.pdf
https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fchem.200802672
https://www.ncbi.nlm.nih.gov/pubmed/19551773
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Volume 15
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