Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni-2(4,4 '-bipyridine)(3)(NO3)(4): guest modification of host sorption behavior

A.J. Fletcher, E.J. Cussen, T.J. Prior, M.J. Rosseinsky, C.J. Kepert, K.M. Thomas

Research output: Contribution to journalArticle

277 Citations (Scopus)

Abstract

This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20% of the total pore volume and at approximately 70% of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a compensation effect. The results are discussed in terms of reversible adsorbate/adsorbent (guest/host) structural changes and interactions and the adsorption mechanism. The paper contains the first evidence of specific interactions between guests and functional groups leading to structural change in flexible porous coordination polymer frameworks.
LanguageEnglish
Pages10001-10011
Number of pages10
JournalJournal of the American Chemical Society
Volume123
Issue number41
DOIs
Publication statusPublished - Oct 2001

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Adsorption
Sorption
Gases
Metals
Vapors
Methanol
Isotherms
Ethanol
Carbon Dioxide
Adsorbents
Carbon dioxide
Nitrous Oxide
X-Ray Diffraction
4,4'-bipyridyl
Activation energy
Pressure
Kinetics
Oxides
Argon
X ray crystallography

Keywords

  • adsorption dynamics
  • gases
  • vapors
  • nanoporous metal
  • organic framework material
  • sorption behavior
  • chemical engineering

Cite this

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title = "Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni-2(4,4 '-bipyridine)(3)(NO3)(4): guest modification of host sorption behavior",
abstract = "This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20{\%} of the total pore volume and at approximately 70{\%} of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a compensation effect. The results are discussed in terms of reversible adsorbate/adsorbent (guest/host) structural changes and interactions and the adsorption mechanism. The paper contains the first evidence of specific interactions between guests and functional groups leading to structural change in flexible porous coordination polymer frameworks.",
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author = "A.J. Fletcher and E.J. Cussen and T.J. Prior and M.J. Rosseinsky and C.J. Kepert and K.M. Thomas",
year = "2001",
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Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni-2(4,4 '-bipyridine)(3)(NO3)(4): guest modification of host sorption behavior. / Fletcher, A.J.; Cussen, E.J.; Prior, T.J.; Rosseinsky, M.J.; Kepert, C.J.; Thomas, K.M.

In: Journal of the American Chemical Society, Vol. 123, No. 41, 10.2001, p. 10001-10011.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni-2(4,4 '-bipyridine)(3)(NO3)(4): guest modification of host sorption behavior

AU - Fletcher, A.J.

AU - Cussen, E.J.

AU - Prior, T.J.

AU - Rosseinsky, M.J.

AU - Kepert, C.J.

AU - Thomas, K.M.

PY - 2001/10

Y1 - 2001/10

N2 - This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20% of the total pore volume and at approximately 70% of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a compensation effect. The results are discussed in terms of reversible adsorbate/adsorbent (guest/host) structural changes and interactions and the adsorption mechanism. The paper contains the first evidence of specific interactions between guests and functional groups leading to structural change in flexible porous coordination polymer frameworks.

AB - This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20% of the total pore volume and at approximately 70% of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a compensation effect. The results are discussed in terms of reversible adsorbate/adsorbent (guest/host) structural changes and interactions and the adsorption mechanism. The paper contains the first evidence of specific interactions between guests and functional groups leading to structural change in flexible porous coordination polymer frameworks.

KW - adsorption dynamics

KW - gases

KW - vapors

KW - nanoporous metal

KW - organic framework material

KW - sorption behavior

KW - chemical engineering

UR - http://pubs.acs.org/doi/abs/10.1021/ja0109895

UR - http://dx.doi.org/10.1021/ja0109895

U2 - 10.1021/ja0109895

DO - 10.1021/ja0109895

M3 - Article

VL - 123

SP - 10001

EP - 10011

JO - Journal of the American Chemical Society

T2 - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 41

ER -