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New functionalized metal-organic frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): synthesis, characterization, and CO2 adsorption properties

Shyam Prosad Biswas UGent, Danny Vanpoucke, Toon Verstraelen UGent, Matthias Vandichel, Sarah Couck, Karen Leus UGent, Ying-Ya Liu UGent, Michel Waroquier UGent, Veronique Van Speybroeck UGent, Joeri FM Denayer, et al. (2013) JOURNAL OF PHYSICAL CHEMISTRY C. 117(44). p.22784-22796
abstract
Six new functionalized vanadium hydroxo terephthalates [V-III(OH)(BDC-X)]center dot n(guests) (MIL-47(V-III)-X-AS) (BDC = 1,4-benzenedicarboxylate; X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3; AS = as-synthesized) along with the parent MIL-47 were synthesized under rapid microwave-assisted hydrothermal conditions (170 degrees C, 30 min, 150 W). The unreacted H2BDC-X and/or occluded solvent molecules can be removed by thermal activation under vacuum, leading to the empty-pore forms of the title compounds (MIL-47(V-IV)-X). Except pristine MIL-47 (+III oxidation state), the vanadium atoms in all the evacuated functionalized solids stayed in the +IV oxidation state. The phase purity of the compounds was ascertained by X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, Raman, thermogravimetric (TG), and elemental analysis. The structural similarity of the filled and empty-pore forms of the functionalized compounds with the respective forms of parent MIL-47 was verified by cell parameter determination from XRPD data. TGA and temperature-dependent XRPD (TDXRPD) experiments in an air atmosphere indicate high thermal stability in the 330-385 degrees C range. All the thermally activated compounds exhibit significant microporosity (S-BET in the 305-897 m(2) g(-1) range), as verified by the N-2 and CO2 sorption analysis. Among the six functionalized compounds, MIL-47(V-IV)-OCH3 shows the highest CO2 uptake, demonstrating the determining role of functional groups on the CO2 sorption behavior. For this compound and pristine MIL-47(V-IV), Widom particle insertion simulations were performed based on ab initio calculated crystal structures. The theoretical Henry coefficients show a good agreement with the experimental values, and calculated isosurfaces for the local excess chemical potential indicate the enhanced CO2 affinity is due to two effects: (i) the interaction between the methoxy group and CO2 and (ii) the collapse of the MIL-47(V-IV)-OCH3 framework.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
CO2, CH4, MOLECULAR-DYNAMICS SIMULATIONS, CANONICAL MONTE-CARLO, EXTENDING HIRSHFELD-I, AUGMENTED-WAVE METHOD, SOLUTION THEORY IAST, CARBON-DIOXIDE, AB-INITIO, GAS-ADSORPTION, PERIODIC MATERIALS, POROUS SOLIDS, breathing, sorption, functionalized MIL-47, MIL-47, Metal-Organic Framework, MOF
journal title
JOURNAL OF PHYSICAL CHEMISTRY C
J. Phys. Chem. C
volume
117
issue
44
pages
22784 - 22796
Web of Science type
Article
Web of Science id
000326845400037
JCR category
MATERIALS SCIENCE, MULTIDISCIPLINARY
JCR impact factor
4.835 (2013)
JCR rank
29/251 (2013)
JCR quartile
1 (2013)
ISSN
1932-7447
DOI
10.1021/jp406835n
project
UGent GOA 01G00710
project
FP7(2007-2013) ERC 240483
project
Methusalem 01M00409
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
4207694
handle
http://hdl.handle.net/1854/LU-4207694
date created
2013-12-12 12:13:18
date last changed
2018-01-29 12:12:00
@article{4207694,
  abstract     = {Six new functionalized vanadium hydroxo terephthalates [V-III(OH)(BDC-X)]center dot n(guests) (MIL-47(V-III)-X-AS) (BDC = 1,4-benzenedicarboxylate; X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3; AS = as-synthesized) along with the parent MIL-47 were synthesized under rapid microwave-assisted hydrothermal conditions (170 degrees C, 30 min, 150 W). The unreacted H2BDC-X and/or occluded solvent molecules can be removed by thermal activation under vacuum, leading to the empty-pore forms of the title compounds (MIL-47(V-IV)-X). Except pristine MIL-47 (+III oxidation state), the vanadium atoms in all the evacuated functionalized solids stayed in the +IV oxidation state. The phase purity of the compounds was ascertained by X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, Raman, thermogravimetric (TG), and elemental analysis. The structural similarity of the filled and empty-pore forms of the functionalized compounds with the respective forms of parent MIL-47 was verified by cell parameter determination from XRPD data. TGA and temperature-dependent XRPD (TDXRPD) experiments in an air atmosphere indicate high thermal stability in the 330-385 degrees C range. All the thermally activated compounds exhibit significant microporosity (S-BET in the 305-897 m(2) g(-1) range), as verified by the N-2 and CO2 sorption analysis. Among the six functionalized compounds, MIL-47(V-IV)-OCH3 shows the highest CO2 uptake, demonstrating the determining role of functional groups on the CO2 sorption behavior. For this compound and pristine MIL-47(V-IV), Widom particle insertion simulations were performed based on ab initio calculated crystal structures. The theoretical Henry coefficients show a good agreement with the experimental values, and calculated isosurfaces for the local excess chemical potential indicate the enhanced CO2 affinity is due to two effects: (i) the interaction between the methoxy group and CO2 and (ii) the collapse of the MIL-47(V-IV)-OCH3 framework.},
  author       = {Biswas, Shyam Prosad and Vanpoucke, Danny and Verstraelen, Toon and Vandichel, Matthias and Couck, Sarah and Leus, Karen and Liu, Ying-Ya and Waroquier, Michel and Van Speybroeck, Veronique and Denayer, Joeri FM and Van Der Voort, Pascal},
  issn         = {1932-7447},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY C},
  keyword      = {CO2,CH4,MOLECULAR-DYNAMICS SIMULATIONS,CANONICAL MONTE-CARLO,EXTENDING HIRSHFELD-I,AUGMENTED-WAVE METHOD,SOLUTION THEORY IAST,CARBON-DIOXIDE,AB-INITIO,GAS-ADSORPTION,PERIODIC MATERIALS,POROUS SOLIDS,breathing,sorption,functionalized MIL-47,MIL-47,Metal-Organic Framework,MOF},
  language     = {eng},
  number       = {44},
  pages        = {22784--22796},
  title        = {New functionalized metal-organic frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): synthesis, characterization, and CO2 adsorption properties},
  url          = {http://dx.doi.org/10.1021/jp406835n},
  volume       = {117},
  year         = {2013},
}

Chicago
Biswas, Shyam Prosad, Danny Vanpoucke, Toon Verstraelen, Matthias Vandichel, Sarah Couck, Karen Leus, Ying-Ya Liu, et al. 2013. “New Functionalized Metal-organic Frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): Synthesis, Characterization, and CO2 Adsorption Properties.” Journal of Physical Chemistry C 117 (44): 22784–22796.
APA
Biswas, S. P., Vanpoucke, D., Verstraelen, T., Vandichel, M., Couck, S., Leus, K., Liu, Y.-Y., et al. (2013). New functionalized metal-organic frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): synthesis, characterization, and CO2 adsorption properties. JOURNAL OF PHYSICAL CHEMISTRY C, 117(44), 22784–22796.
Vancouver
1.
Biswas SP, Vanpoucke D, Verstraelen T, Vandichel M, Couck S, Leus K, et al. New functionalized metal-organic frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): synthesis, characterization, and CO2 adsorption properties. JOURNAL OF PHYSICAL CHEMISTRY C. 2013;117(44):22784–96.
MLA
Biswas, Shyam Prosad, Danny Vanpoucke, Toon Verstraelen, et al. “New Functionalized Metal-organic Frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): Synthesis, Characterization, and CO2 Adsorption Properties.” JOURNAL OF PHYSICAL CHEMISTRY C 117.44 (2013): 22784–22796. Print.