Jump to main content
Jump to site search

Issue 5, 2012
Previous Article Next Article

H2storage in isostructural UiO-67 and UiO-66 MOFs

Author affiliations

Abstract

The recently discovered UiO-66/67/68 class of isostructural metallorganic frameworks (MOFs) [J. H. Cavka et al. J. Am. Chem. Soc., 2008, 130, 13850] has attracted great interest because of its remarkable stability at high temperatures, high pressures and in the presence of different solvents, acids and bases [L. Valenzano et al. Chem. Mater., 2011, 23, 1700]. UiO-66 is obtained by connecting Zr6O4(OH)4 inorganic cornerstones with 1,4-benzene-dicarboxylate (BDC) as linker resulting in a cubic MOF, which has already been successfully reproduced in several laboratories. Here we report the first complete structural, vibrational and electronic characterization of the isostructural UiO-67 material, obtained using the longer 4,4′-biphenyl-dicarboxylate (BPDC) linker, by combining laboratory XRPD, Zr K-edge EXAFS, TGA, FTIR, and UV-Vis studies. Comparison between experimental and periodic calculations performed at the B3LYP level of theory allows a full understanding of the structural, vibrational and electronic properties of the material. Both materials have been tested for molecular hydrogen storage at high pressures and at liquid nitrogen temperature. In this regard, the use of a longer ligand has a double benefit: (i) it reduces the density of the material and (ii) it increases the Langmuir surface area from 1281 to 2483 m2 g−1 and the micropore volume from 0.43 to 0.85 cm3 g−1. As a consequence, the H2 uptake at 38 bar and 77 K increases from 2.4 mass% for UiO-66 up to 4.6 mass% for the new UiO-67 material. This value is among the highest values reported so far but is lower than those reported for MIL-101, IRMOF-20 and MOF-177 under similar pressure and temperature conditions (6.1, 6.2 and 7.0 mass%, respectively) [A. G. Wong-Foy et al. J. Am. Chem. Soc., 2006, 128, 3494; M. Dinca and J. R. Long. Angew. Chem., Int. Ed., 2008, 47, 6766]. Nevertheless the remarkable chemical and thermal stability of UiO-67 and the absence of Cr in its structure would make this material competitive.

Graphical abstract: H2storage in isostructural UiO-67 and UiO-66 MOFs

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 11 Aug 2011, accepted on 14 Nov 2011 and first published on 20 Dec 2011


Article type: Paper
DOI: 10.1039/C1CP23434J
Citation: Phys. Chem. Chem. Phys., 2012,14, 1614-1626
  •   Request permissions

    H2storage in isostructural UiO-67 and UiO-66 MOFs

    S. Chavan, J. G. Vitillo, D. Gianolio, O. Zavorotynska, B. Civalleri, S. Jakobsen, M. H. Nilsen, L. Valenzano, C. Lamberti, K. P. Lillerud and S. Bordiga, Phys. Chem. Chem. Phys., 2012, 14, 1614
    DOI: 10.1039/C1CP23434J

Search articles by author