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Correlating MOF-808 parameters with mixed-matrix membrane (MMM) CO2 permeation for a more rational MMM development

Raymond Thür, Daan Van Havere, Niels Van Velthoven, Simon Smolders, Aran Lamaire (UGent) , Jelle Wieme (UGent) , Veronique Van Speybroeck (UGent) , Dirk De Vos and Ivo F. J. Vankelecom
(2021) JOURNAL OF MATERIALS CHEMISTRY A. 9(21). p.12782-12796
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Abstract
Consistent structure-performance relationships for the design of MOF (metal-organic framework)-based mixed-matrix membranes (MMMs) for gas separation are currently scarce in MMM literature. An important step in establishing such relationships could be to correlate intrinsic MOF parameters, such as CO2 uptake and the CO2 adsorption enthalpy (Q(st)), with the separation performance indicators of the MMM (i.e. separation factor and permeability). Such a study presumes the availability of a platform MOF, which allows systematic comparison of the relevant MOF parameters. MOF-808 can take up the role of such a platform MOF, owing to its unique cluster coordination and subsequent ease of introducing additional functional molecules. For this purpose, formic acid (FA) modulated MOF-808 (MOF-FA) was post-synthetically functionalized with five different ligands (histidine (His), benzoic acid (BA), glycolic acid (GA), lithium sulfate (Li2SO4) and trifluoroacetic acid (TFA)) to create a series of isostructural MOFs with varying affinity/diffusivity properties but as constant as possible remaining properties (e.g. particles size distribution). CO2 uptake and CO2 adsorption enthalpy of the MOFs were determined with CO2 sorption experiments and Clausius-Clapeyron analysis. These MOF properties were subsequently linked to the CO2/N-2 separation factor and CO2 permeability of the corresponding MMM. Unlike what is often assumed in literature, MOF-808 CO2 uptake proved to be a poor indicator for MMM performance. In contrast, a strong correlation was observed between Q(st) at high CO2 loadings on one hand and CO2 permeability under varying feed conditions on the other hand. Furthermore, correlation coefficients of Q(st,15) and Q(st,30) (Q(st) at 15 and 30 cm(3) (STP) g(-1)) with the separation factor were significantly better than those calculated for CO2 uptake. The surprising lack of correlation between membrane performance and CO2 uptake and the strong correlation with Q(st) opens possibilities to rationally design MMMs and stresses the need for more fundamental research focused on finding consistent relationships between filler properties and the final membrane performance.
Keywords
Renewable Energy, Sustainability and the Environment, General Materials Science, General Chemistry

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MLA
Thür, Raymond, et al. “Correlating MOF-808 Parameters with Mixed-Matrix Membrane (MMM) CO2 Permeation for a More Rational MMM Development.” JOURNAL OF MATERIALS CHEMISTRY A, vol. 9, no. 21, 2021, pp. 12782–96, doi:10.1039/d0ta10207e.
APA
Thür, R., Van Havere, D., Van Velthoven, N., Smolders, S., Lamaire, A., Wieme, J., … Vankelecom, I. F. J. (2021). Correlating MOF-808 parameters with mixed-matrix membrane (MMM) CO2 permeation for a more rational MMM development. JOURNAL OF MATERIALS CHEMISTRY A, 9(21), 12782–12796. https://doi.org/10.1039/d0ta10207e
Chicago author-date
Thür, Raymond, Daan Van Havere, Niels Van Velthoven, Simon Smolders, Aran Lamaire, Jelle Wieme, Veronique Van Speybroeck, Dirk De Vos, and Ivo F. J. Vankelecom. 2021. “Correlating MOF-808 Parameters with Mixed-Matrix Membrane (MMM) CO2 Permeation for a More Rational MMM Development.” JOURNAL OF MATERIALS CHEMISTRY A 9 (21): 12782–96. https://doi.org/10.1039/d0ta10207e.
Chicago author-date (all authors)
Thür, Raymond, Daan Van Havere, Niels Van Velthoven, Simon Smolders, Aran Lamaire, Jelle Wieme, Veronique Van Speybroeck, Dirk De Vos, and Ivo F. J. Vankelecom. 2021. “Correlating MOF-808 Parameters with Mixed-Matrix Membrane (MMM) CO2 Permeation for a More Rational MMM Development.” JOURNAL OF MATERIALS CHEMISTRY A 9 (21): 12782–12796. doi:10.1039/d0ta10207e.
Vancouver
1.
Thür R, Van Havere D, Van Velthoven N, Smolders S, Lamaire A, Wieme J, et al. Correlating MOF-808 parameters with mixed-matrix membrane (MMM) CO2 permeation for a more rational MMM development. JOURNAL OF MATERIALS CHEMISTRY A. 2021;9(21):12782–96.
IEEE
[1]
R. Thür et al., “Correlating MOF-808 parameters with mixed-matrix membrane (MMM) CO2 permeation for a more rational MMM development,” JOURNAL OF MATERIALS CHEMISTRY A, vol. 9, no. 21, pp. 12782–12796, 2021.
@article{8714129,
  abstract     = {{Consistent structure-performance relationships for the design of MOF (metal-organic framework)-based mixed-matrix membranes (MMMs) for gas separation are currently scarce in MMM literature. An important step in establishing such relationships could be to correlate intrinsic MOF parameters, such as CO2 uptake and the CO2 adsorption enthalpy (Q(st)), with the separation performance indicators of the MMM (i.e. separation factor and permeability). Such a study presumes the availability of a platform MOF, which allows systematic comparison of the relevant MOF parameters. MOF-808 can take up the role of such a platform MOF, owing to its unique cluster coordination and subsequent ease of introducing additional functional molecules. For this purpose, formic acid (FA) modulated MOF-808 (MOF-FA) was post-synthetically functionalized with five different ligands (histidine (His), benzoic acid (BA), glycolic acid (GA), lithium sulfate (Li2SO4) and trifluoroacetic acid (TFA)) to create a series of isostructural MOFs with varying affinity/diffusivity properties but as constant as possible remaining properties (e.g. particles size distribution). CO2 uptake and CO2 adsorption enthalpy of the MOFs were determined with CO2 sorption experiments and Clausius-Clapeyron analysis. These MOF properties were subsequently linked to the CO2/N-2 separation factor and CO2 permeability of the corresponding MMM. Unlike what is often assumed in literature, MOF-808 CO2 uptake proved to be a poor indicator for MMM performance. In contrast, a strong correlation was observed between Q(st) at high CO2 loadings on one hand and CO2 permeability under varying feed conditions on the other hand. Furthermore, correlation coefficients of Q(st,15) and Q(st,30) (Q(st) at 15 and 30 cm(3) (STP) g(-1)) with the separation factor were significantly better than those calculated for CO2 uptake. The surprising lack of correlation between membrane performance and CO2 uptake and the strong correlation with Q(st) opens possibilities to rationally design MMMs and stresses the need for more fundamental research focused on finding consistent relationships between filler properties and the final membrane performance.}},
  author       = {{Thür, Raymond and Van Havere, Daan and Van Velthoven, Niels and Smolders, Simon and Lamaire, Aran and Wieme, Jelle and Van Speybroeck, Veronique and De Vos, Dirk and Vankelecom, Ivo F. J.}},
  issn         = {{2050-7488}},
  journal      = {{JOURNAL OF MATERIALS CHEMISTRY A}},
  keywords     = {{Renewable Energy,Sustainability and the Environment,General Materials Science,General Chemistry}},
  language     = {{eng}},
  number       = {{21}},
  pages        = {{12782--12796}},
  title        = {{Correlating MOF-808 parameters with mixed-matrix membrane (MMM) CO2 permeation for a more rational MMM development}},
  url          = {{http://dx.doi.org/10.1039/d0ta10207e}},
  volume       = {{9}},
  year         = {{2021}},
}
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