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Title: Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

Abstract

Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even aftermore » hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.« less

Authors:
;  [1];  [1];  [2];  [1]; ;  [3];  [1];  [2];  [2]
  1. Laboratory for Inorganic Chemistry and Technology, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana (Slovenia)
  2. (Slovenia)
  3. Institut Lavoisier, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles (France)
Publication Date:
OSTI Identifier:
22475596
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 225; 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; ABSORPTION SPECTROSCOPY; ACETYLACETONE; ADSORPTION; CAPACITY; CARBON 13; COVALENCE; ENTHALPY; HYDROGEN 1; LIGANDS; MAGNESIUM COMPLEXES; MAGNESIUM COMPOUNDS; MOLECULES; NICKEL COMPOUNDS; NMR SPECTRA; NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; VAN DER WAALS FORCES; ZIRCONIUM COMPOUNDS

Citation Formats

Žunkovič, E., Mazaj, M., Mali, G., EN-FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Rangus, M., Devic, T., Serre, C., Logar, N. Zabukovec, E-mail: natasa.zabukovec@ki.si, CO-NOT Centre of Excellence, Hajdrihova 19, 1000 Ljubljana, and University of Nova Gorica, Vipavska 13, 5000 Nova Gorica. Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2014.12.033.
Žunkovič, E., Mazaj, M., Mali, G., EN-FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Rangus, M., Devic, T., Serre, C., Logar, N. Zabukovec, E-mail: natasa.zabukovec@ki.si, CO-NOT Centre of Excellence, Hajdrihova 19, 1000 Ljubljana, & University of Nova Gorica, Vipavska 13, 5000 Nova Gorica. Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties. United States. doi:10.1016/J.JSSC.2014.12.033.
Žunkovič, E., Mazaj, M., Mali, G., EN-FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Rangus, M., Devic, T., Serre, C., Logar, N. Zabukovec, E-mail: natasa.zabukovec@ki.si, CO-NOT Centre of Excellence, Hajdrihova 19, 1000 Ljubljana, and University of Nova Gorica, Vipavska 13, 5000 Nova Gorica. Fri . "Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties". United States. doi:10.1016/J.JSSC.2014.12.033.
@article{osti_22475596,
title = {Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties},
author = {Žunkovič, E. and Mazaj, M. and Mali, G. and EN-FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana and Rangus, M. and Devic, T. and Serre, C. and Logar, N. Zabukovec, E-mail: natasa.zabukovec@ki.si and CO-NOT Centre of Excellence, Hajdrihova 19, 1000 Ljubljana and University of Nova Gorica, Vipavska 13, 5000 Nova Gorica},
abstractNote = {Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.},
doi = {10.1016/J.JSSC.2014.12.033},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 225,
place = {United States},
year = {2015},
month = {5}
}