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Title: Biporous Metal–Organic Framework with Tunable CO 2 /CH 4 Separation Performance Facilitated by Intrinsic Flexibility

Abstract

In this work, we report the synthesis of SION-8, a novel metal-organic framework (MOF) based on Ca(II) and a tetracarboxylate ligand TBAPy4- endowed with two chemically distinct types of pores characterized by their hydrophobic and hydrophilic properties. By altering the activation conditions, we gained access to two bulk materials: the fully activated SION-8F and the partially activated SION-8P with exclusively the hydrophobic pores activated. SION-8P shows high affinity for both CO2 (Qst = 28.4 kJ/mol) and CH4 (Qst = 21.4 kJ/mol), while upon full activation, the difference in affinity for CO2 (Qst = 23.4 kJ/mol) and CH4 (Qst = 16.0 kJ/mol) is more pronounced. The intrinsic flexibility of both materials results in complex adsorption behavior and greater adsorption of gas molecules than if the materials were rigid. Their CO2/CH4 separation performance was tested in fixed-bed breakthrough experiments using binary gas mixtures of different compositions and rationalized in terms of molecular interactions. SION-8F showed a 40-160% increase (depending on the temperature and the gas mixture composition probed) of the CO2/CH4 dynamic breakthrough selectivity compared to SION-8P, demonstrating the possibility to rationally tune the separation performance of a single MOF by manipulating the stepwise activation made possible by the MOF’s biporous nature

Authors:
 [1];  [2]; ORCiD logo [3];  [1];  [4]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [1]
  1. Laboratory of Molecular Simulation (LSMO), Institut des sciences et ingénierie chimiques (ISIC), École polytechnique fédérale de Lausanne (EPFL) Valais, Rue de l’Industrie 17, 1951 Sion, Switzerland
  2. Department of Chemistry, University of California, Berkeley, California 94720, United States
  3. Swiss-Norwegian Beamlines, European Synchrotron Radiation Facility, 38000 Grenoble, France
  4. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
  5. Departamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071 Granada, Spain
  6. Laboratory of Molecular Simulation (LSMO), Institut des sciences et ingénierie chimiques (ISIC), École polytechnique fédérale de Lausanne (EPFL) Valais, Rue de l’Industrie 17, 1951 Sion, Switzerland, Department of Chemistry, University of California, Berkeley, California 94720, United States, Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Ecole Polytechnique Federale Lausanne (EPFL) (Switzerland)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1478678
Alternate Identifier(s):
OSTI ID: 1508739
Grant/Contract Number:  
SC0001015; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Name: ACS Applied Materials and Interfaces Journal Volume: 10 Journal Issue: 42; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal−organic frameworks; biporous MOFs; gas adsorption; breakthrough curves; CO2/CH4 separation

Citation Formats

Gładysiak, Andrzej, Deeg, Kathryn S., Dovgaliuk, Iurii, Chidambaram, Arunraj, Ordiz, Kaili, Boyd, Peter G., Moosavi, Seyed Mohamad, Ongari, Daniele, Navarro, Jorge A. R., Smit, Berend, and Stylianou, Kyriakos C. Biporous Metal–Organic Framework with Tunable CO 2 /CH 4 Separation Performance Facilitated by Intrinsic Flexibility. United States: N. p., 2018. Web. doi:10.1021/acsami.8b13362.
Gładysiak, Andrzej, Deeg, Kathryn S., Dovgaliuk, Iurii, Chidambaram, Arunraj, Ordiz, Kaili, Boyd, Peter G., Moosavi, Seyed Mohamad, Ongari, Daniele, Navarro, Jorge A. R., Smit, Berend, & Stylianou, Kyriakos C. Biporous Metal–Organic Framework with Tunable CO 2 /CH 4 Separation Performance Facilitated by Intrinsic Flexibility. United States. https://doi.org/10.1021/acsami.8b13362
Gładysiak, Andrzej, Deeg, Kathryn S., Dovgaliuk, Iurii, Chidambaram, Arunraj, Ordiz, Kaili, Boyd, Peter G., Moosavi, Seyed Mohamad, Ongari, Daniele, Navarro, Jorge A. R., Smit, Berend, and Stylianou, Kyriakos C. Mon . "Biporous Metal–Organic Framework with Tunable CO 2 /CH 4 Separation Performance Facilitated by Intrinsic Flexibility". United States. https://doi.org/10.1021/acsami.8b13362.
@article{osti_1478678,
title = {Biporous Metal–Organic Framework with Tunable CO 2 /CH 4 Separation Performance Facilitated by Intrinsic Flexibility},
author = {Gładysiak, Andrzej and Deeg, Kathryn S. and Dovgaliuk, Iurii and Chidambaram, Arunraj and Ordiz, Kaili and Boyd, Peter G. and Moosavi, Seyed Mohamad and Ongari, Daniele and Navarro, Jorge A. R. and Smit, Berend and Stylianou, Kyriakos C.},
abstractNote = {In this work, we report the synthesis of SION-8, a novel metal-organic framework (MOF) based on Ca(II) and a tetracarboxylate ligand TBAPy4- endowed with two chemically distinct types of pores characterized by their hydrophobic and hydrophilic properties. By altering the activation conditions, we gained access to two bulk materials: the fully activated SION-8F and the partially activated SION-8P with exclusively the hydrophobic pores activated. SION-8P shows high affinity for both CO2 (Qst = 28.4 kJ/mol) and CH4 (Qst = 21.4 kJ/mol), while upon full activation, the difference in affinity for CO2 (Qst = 23.4 kJ/mol) and CH4 (Qst = 16.0 kJ/mol) is more pronounced. The intrinsic flexibility of both materials results in complex adsorption behavior and greater adsorption of gas molecules than if the materials were rigid. Their CO2/CH4 separation performance was tested in fixed-bed breakthrough experiments using binary gas mixtures of different compositions and rationalized in terms of molecular interactions. SION-8F showed a 40-160% increase (depending on the temperature and the gas mixture composition probed) of the CO2/CH4 dynamic breakthrough selectivity compared to SION-8P, demonstrating the possibility to rationally tune the separation performance of a single MOF by manipulating the stepwise activation made possible by the MOF’s biporous nature},
doi = {10.1021/acsami.8b13362},
journal = {ACS Applied Materials and Interfaces},
number = 42,
volume = 10,
place = {United States},
year = {Mon Sep 24 00:00:00 EDT 2018},
month = {Mon Sep 24 00:00:00 EDT 2018}
}

Journal Article:
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https://doi.org/10.1021/acsami.8b13362

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