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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 TBAPy 4- 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 CO 2 (Q st = 28.4 kJ/mol) and CH 4 (Q st = 21.4 kJ/mol), while upon full activation, the difference in affinity for CO 2 (Q st = 23.4 kJ/mol) and CH 4 (Q st = 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 CO 2/CH 4 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 CO 2/CH 4 dynamic breakthrough selectivity compared to SION-8P, demonstrating the possibility to rationally tune the separation performance of a singlemore » MOF by manipulating the stepwise activation made possible by the MOF’s biporous nature« less

Authors:
 [1];  [2];  [3];  [1];  [4]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [1]
  1. Ecole Polytechnique Federale Lausanne (Switzlerland). Lab. of Molecular Simulation (LSMO), Inst. des sciences et ingénierie chimiques (ISIC)
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. European Synchrotron Radiation Facility (ESRF), Grenoble (France). Swiss-Norwegian Beamlines
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  5. Univ. de Granada, Granada (Spain). Dept. de Química Inorgánica
  6. Ecole Polytechnique Federale Lausanne (Switzlerland). Lab. of Molecular Simulation (LSMO), Inst. des sciences et ingénierie chimiques (ISIC); Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, and Dept. of Chemical and Biomolecular Engineering
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 (Switzlerland)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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 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., Deeg, Kathryn S., 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., Deeg, Kathryn S., 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. doi:10.1021/acsami.8b13362.
Gładysiak, Andrzej, Deeg, Kathryn S., Deeg, Kathryn S., 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. doi: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 Deeg, Kathryn S. 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 = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acsami.8b13362

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Cited by: 8 works
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