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Title: Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework

Abstract

The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr{sub 6}O{sub 4}(OH){sub 4}(DMTDC){sub 6}]·4.8DMF·10H{sub 2}O (1) (H{sub 2}DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl{sub 4}, H{sub 2}DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl{sub 4}/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achieved by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N{sub 2} and CO{sub 2} sorption analyses suggest that the material possesses remarkably high microporosity (S{sub BET}=1236 m{sup 2} g{sup −1}; CO{sub 2} uptake=3.5more » mmol g{sup −1} at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N{sub 2} and CO{sub 2} sorption experiments revealed significantly high microporosity. • The material showed high adsorption selectivity for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions.« less

Authors:
 [1]; ;  [2];  [1]
  1. Department of Chemistry, Indian Institute of Technology Guwahati, 781039 Assam (India)
  2. Institute of Physics, Chair of Solid State Science, Augsburg University, Universitätsstrasse 1, D-86135 Augsburg (Germany)
Publication Date:
OSTI Identifier:
22573981
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 232; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADSORPTION; BENZOIC ACID; CARBON DIOXIDE; CATIONS; COBALT IONS; COPPER IONS; DICARBOXYLIC ACIDS; FOURIER TRANSFORMATION; INFRARED SPECTRA; LIGANDS; NICKEL IONS; ORGANOMETALLIC COMPOUNDS; POLYCYCLIC SULFUR HETEROCYCLES; SOLUTIONS; SYNTHESIS; THERMAL GRAVIMETRIC ANALYSIS; THIOPHENE; X-RAY DIFFRACTION; ZIRCONIUM; ZIRCONIUM CHLORIDES

Citation Formats

SK, Mostakim, Grzywa, Maciej, Volkmer, Dirk, and Biswas, Shyam. Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2015.09.034.
SK, Mostakim, Grzywa, Maciej, Volkmer, Dirk, & Biswas, Shyam. Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework. United States. doi:10.1016/J.JSSC.2015.09.034.
SK, Mostakim, Grzywa, Maciej, Volkmer, Dirk, and Biswas, Shyam. Tue . "Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework". United States. doi:10.1016/J.JSSC.2015.09.034.
@article{osti_22573981,
title = {Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework},
author = {SK, Mostakim and Grzywa, Maciej and Volkmer, Dirk and Biswas, Shyam},
abstractNote = {The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr{sub 6}O{sub 4}(OH){sub 4}(DMTDC){sub 6}]·4.8DMF·10H{sub 2}O (1) (H{sub 2}DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl{sub 4}, H{sub 2}DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl{sub 4}/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achieved by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N{sub 2} and CO{sub 2} sorption analyses suggest that the material possesses remarkably high microporosity (S{sub BET}=1236 m{sup 2} g{sup −1}; CO{sub 2} uptake=3.5 mmol g{sup −1} at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N{sub 2} and CO{sub 2} sorption experiments revealed significantly high microporosity. • The material showed high adsorption selectivity for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions.},
doi = {10.1016/J.JSSC.2015.09.034},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 232,
place = {United States},
year = {2015},
month = {12}
}