Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture

Marvin Benzaqui; Renjith S. Pillai; Anahid Sabetghadam; Virginie Benoit; Perine Normand; Jérôme Marrot; Nicolas Menguy; David Montero; William Shepard; Antoine Tissot; Charlotte Martineau-Corcos; Clémence Sicard; Mihail Mihaylov; Florent Carn; Isabelle Beurroies; Philip L. Llewellyn; Guy De Weireld; Konstantin Hadjiivanov; Jorge Gascon; Freek Kapteijn; Guillaume Maurin; Nathalie Steunou; Christian Serre

doi:10.1021/acs.chemmater.7b03203

Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO₂ Capture

Marvin Benzaqui, Renjith S. Pillai, Anahid Sabetghadam, Virginie Benoit, Perine Normand, Jérôme Marrot, Nicolas Menguy, David Montero, William Shepard, Antoine Tissot, Charlotte Martineau-Corcos, Clémence Sicard, Mihail Mihaylov, Florent Carn, Isabelle Beurroies, Philip L. Llewellyn, Guy De Weireld, Konstantin Hadjiivanov, Jorge Gascon, Freek KapteijnGuillaume Maurin, Nathalie Steunou^*, Christian Serre

^*Corresponding author for this work

Chemical Engineering

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

84 Scopus citations

Abstract

A microporous Al trimesate-based metal-organic framework (MOF), denoted MIL-96-(Al), was selected as a porous hybrid filler for the processing of mixed matrix membranes (MMMs) for CO₂/N₂ postcombustion separation. First, the structural model of MIL-96-(Al) initially reported was revisited using a combination of synchrotron-based single-crystal X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations. In a second step, pure MIL-96-(Al) crystals differing by their size and aspect ratio, including anisotropic hexagonal platelets and nanoparticles of about 70 nm in diameter, were prepared. Then, a combination of in situ IR spectroscopy, single-gas, and CO₂/N₂ coadsorption experiments, calorimetry, and molecular simulations revealed that MIL-96-(Al) nanoparticles show a relatively high CO₂ affinity over N₂ owing to strong interactions between CO₂ molecules and several adsorption sites such as Al³⁺ Lewis centers, coordinated water, and hydroxyl groups. Finally, the high compatibility between MIL-96-(Al) nanoparticles and the 6FDA-DAM polymer allowed the processing of homogeneous and defect-free MMMs with a high MOF loading (up to 25 wt %) that outperform pure polymer membranes for CO₂/N₂ separation.

Original language	English (US)
Pages (from-to)	10326-10338
Number of pages	13
Journal	Chemistry of Materials
Volume	29
Issue number	24
DOIs	https://doi.org/10.1021/acs.chemmater.7b03203
State	Published - Dec 26 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.7b03203

Cite this

Benzaqui, M., Pillai, R. S., Sabetghadam, A., Benoit, V., Normand, P., Marrot, J., Menguy, N., Montero, D., Shepard, W., Tissot, A., Martineau-Corcos, C., Sicard, C., Mihaylov, M., Carn, F., Beurroies, I., Llewellyn, P. L., De Weireld, G., Hadjiivanov, K., Gascon, J., ... Serre, C. (2017). Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO₂ Capture. Chemistry of Materials, 29(24), 10326-10338. https://doi.org/10.1021/acs.chemmater.7b03203

@article{abe07fd123d4456ca1328ff5381bc04e,

title = "Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture",

abstract = "A microporous Al trimesate-based metal-organic framework (MOF), denoted MIL-96-(Al), was selected as a porous hybrid filler for the processing of mixed matrix membranes (MMMs) for CO2/N2 postcombustion separation. First, the structural model of MIL-96-(Al) initially reported was revisited using a combination of synchrotron-based single-crystal X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations. In a second step, pure MIL-96-(Al) crystals differing by their size and aspect ratio, including anisotropic hexagonal platelets and nanoparticles of about 70 nm in diameter, were prepared. Then, a combination of in situ IR spectroscopy, single-gas, and CO2/N2 coadsorption experiments, calorimetry, and molecular simulations revealed that MIL-96-(Al) nanoparticles show a relatively high CO2 affinity over N2 owing to strong interactions between CO2 molecules and several adsorption sites such as Al3+ Lewis centers, coordinated water, and hydroxyl groups. Finally, the high compatibility between MIL-96-(Al) nanoparticles and the 6FDA-DAM polymer allowed the processing of homogeneous and defect-free MMMs with a high MOF loading (up to 25 wt %) that outperform pure polymer membranes for CO2/N2 separation.",

author = "Marvin Benzaqui and Pillai, {Renjith S.} and Anahid Sabetghadam and Virginie Benoit and Perine Normand and J{\'e}r{\^o}me Marrot and Nicolas Menguy and David Montero and William Shepard and Antoine Tissot and Charlotte Martineau-Corcos and Cl{\'e}mence Sicard and Mihail Mihaylov and Florent Carn and Isabelle Beurroies and Llewellyn, {Philip L.} and {De Weireld}, Guy and Konstantin Hadjiivanov and Jorge Gascon and Freek Kapteijn and Guillaume Maurin and Nathalie Steunou and Christian Serre",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = dec,

day = "26",

doi = "10.1021/acs.chemmater.7b03203",

language = "English (US)",

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Benzaqui, M, Pillai, RS, Sabetghadam, A, Benoit, V, Normand, P, Marrot, J, Menguy, N, Montero, D, Shepard, W, Tissot, A, Martineau-Corcos, C, Sicard, C, Mihaylov, M, Carn, F, Beurroies, I, Llewellyn, PL, De Weireld, G, Hadjiivanov, K, Gascon, J, Kapteijn, F, Maurin, G, Steunou, N & Serre, C 2017, 'Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO₂ Capture', Chemistry of Materials, vol. 29, no. 24, pp. 10326-10338. https://doi.org/10.1021/acs.chemmater.7b03203

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T1 - Revisiting the Aluminum Trimesate-Based MOF (MIL-96)

T2 - From Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture

AU - Benzaqui, Marvin

AU - Pillai, Renjith S.

AU - Sabetghadam, Anahid

AU - Benoit, Virginie

AU - Normand, Perine

AU - Marrot, Jérôme

AU - Menguy, Nicolas

AU - Montero, David

AU - Shepard, William

AU - Tissot, Antoine

AU - Martineau-Corcos, Charlotte

AU - Sicard, Clémence

AU - Mihaylov, Mihail

AU - Carn, Florent

AU - Beurroies, Isabelle

AU - Llewellyn, Philip L.

AU - De Weireld, Guy

AU - Hadjiivanov, Konstantin

AU - Gascon, Jorge

AU - Kapteijn, Freek

AU - Maurin, Guillaume

AU - Steunou, Nathalie

AU - Serre, Christian

PY - 2017/12/26

Y1 - 2017/12/26

N2 - A microporous Al trimesate-based metal-organic framework (MOF), denoted MIL-96-(Al), was selected as a porous hybrid filler for the processing of mixed matrix membranes (MMMs) for CO2/N2 postcombustion separation. First, the structural model of MIL-96-(Al) initially reported was revisited using a combination of synchrotron-based single-crystal X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations. In a second step, pure MIL-96-(Al) crystals differing by their size and aspect ratio, including anisotropic hexagonal platelets and nanoparticles of about 70 nm in diameter, were prepared. Then, a combination of in situ IR spectroscopy, single-gas, and CO2/N2 coadsorption experiments, calorimetry, and molecular simulations revealed that MIL-96-(Al) nanoparticles show a relatively high CO2 affinity over N2 owing to strong interactions between CO2 molecules and several adsorption sites such as Al3+ Lewis centers, coordinated water, and hydroxyl groups. Finally, the high compatibility between MIL-96-(Al) nanoparticles and the 6FDA-DAM polymer allowed the processing of homogeneous and defect-free MMMs with a high MOF loading (up to 25 wt %) that outperform pure polymer membranes for CO2/N2 separation.

AB - A microporous Al trimesate-based metal-organic framework (MOF), denoted MIL-96-(Al), was selected as a porous hybrid filler for the processing of mixed matrix membranes (MMMs) for CO2/N2 postcombustion separation. First, the structural model of MIL-96-(Al) initially reported was revisited using a combination of synchrotron-based single-crystal X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations. In a second step, pure MIL-96-(Al) crystals differing by their size and aspect ratio, including anisotropic hexagonal platelets and nanoparticles of about 70 nm in diameter, were prepared. Then, a combination of in situ IR spectroscopy, single-gas, and CO2/N2 coadsorption experiments, calorimetry, and molecular simulations revealed that MIL-96-(Al) nanoparticles show a relatively high CO2 affinity over N2 owing to strong interactions between CO2 molecules and several adsorption sites such as Al3+ Lewis centers, coordinated water, and hydroxyl groups. Finally, the high compatibility between MIL-96-(Al) nanoparticles and the 6FDA-DAM polymer allowed the processing of homogeneous and defect-free MMMs with a high MOF loading (up to 25 wt %) that outperform pure polymer membranes for CO2/N2 separation.

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DO - 10.1021/acs.chemmater.7b03203

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Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO₂ Capture

Abstract

Bibliographical note

ASJC Scopus subject areas

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CCDC 1558833: Experimental Crystal Structure Determination : catena-[hexakis(mu-benzene-1,3,5-tricarboxylato)-dodecakis(mu-hydroxo)-(mu-oxo)-pentaaqua-tetrakis(hydroxy)-dodeca-aluminium hydrate]

Cite this

Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1558833: Experimental Crystal Structure Determination : catena-[hexakis(mu-benzene-1,3,5-tricarboxylato)-dodecakis(mu-hydroxo)-(mu-oxo)-pentaaqua-tetrakis(hydroxy)-dodeca-aluminium hydrate]

Cite this

Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO₂ Capture