H2storage in isostructural UiO-67 and UiO-66 MOFs
| Autor: | Merete Hellner Nilsen, Diego Gianolio, Loredana Valenzano, Olena Zavorotynska, Søren Jakobsen, Jenny G. Vitillo, Bartolomeo Civalleri, Sachin Chavan, Silvia Bordiga, Karl Petter Lillerud, Carlo Lamberti |
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| Rok vydání: | 2012 |
| Předmět: |
Langmuir
General Physics and Astronomy XRPD hydrogen storage Hydrogen storage Computational chemistry Thermal stability Physical and Theoretical Chemistry Isostructural MOF TGA Extended X-ray absorption fine structure Zr ab initio Chemistry UV-Vis Microporous material EXAFS UiO-67 UiO-66 IR BPDC linker BDC linker Physical chemistry Powder diffraction Bar (unit) |
| Zdroj: | Phys. Chem. Chem. Phys.. 14:1614-1626 |
| ISSN: | 1463-9084 1463-9076 |
| Popis: | 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 Zr(6)O(4)(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 m(2) g(-1) and the micropore volume from 0.43 to 0.85 cm(3) g(-1). As a consequence, the H(2) 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. |
| Databáze: | OpenAIRE |
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