Synthesis of MIL-102, a chromium carboxylate metal-organic framework, with gas sorption analysis

Suzy Surblé, Franck Millange, Christian Serre, Tina Düren, Michel Latroche, Sandrine Bourrelly, Philip L. Llewellyn, Gérard Férey

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198 Citations (Scopus)

Abstract

A new three-dimensional chromium(III) naphthalene tetracarboxylate, Cr III 3O(H 2O) 2F{C 10H 4-(CO 2) 4} 1.5·6H 2O (MIL-102), has been synthesized under hydrothermal conditions from an aqueous mixture of Cr(NO 3) 3·9H 2O, naphthalene-1,4,5,8-tetracarboxylic acid, and HF. Its structure, solved ab initio from X-ray powder diffraction data, is built up from the connection of trimers of trivalent chromium octahedra and tetracarboxylate moieties. This creates a three-dimensional structure with an array of small one-dimensional channels filled with free water molecules, which interact through hydrogen bonds with terminal water molecules and oxygen atoms from the carboxylates. Thermogravimetric analysis and X-ray thermodiffractometry indicate that MIL-102 is stable up to ∼300°C and shows zeolitic behavior. Due to topological frustration effects, MIL-102 remains paramagnetic down to 5 K. Finally, MIL-102 exhibits a hydrogen storage capacity of ∼1.0 wt % at 77 K when loaded at 3.5 MPa (35 bar). The hydrogen uptake is discussed in relation with the structural characteristics and the molecular simulation results. The adsorption behavior of MIL-102 at 304 K resembles that of small-pore zeolites, such as silicalite. Indeed, the isotherms of CO 2, CH 4, and N 2 show a maximum uptake at 0.5 MPa, with no further significant adsorption up to 3 MPa. Crystal data for MIL-102: hexagonal space group P6 (No. 169), a = 12.632(1) Å, c = 9.622(1) Å.

Original languageEnglish
Pages (from-to)14889-14896
Number of pages8
JournalJournal of the American Chemical Society
Volume128
Issue number46
Early online date28 Oct 2006
DOIs
Publication statusPublished - 22 Nov 2006

ASJC Scopus subject areas

  • Chemistry(all)

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    Surblé, S., Millange, F., Serre, C., Düren, T., Latroche, M., Bourrelly, S., Llewellyn, P. L., & Férey, G. (2006). Synthesis of MIL-102, a chromium carboxylate metal-organic framework, with gas sorption analysis. Journal of the American Chemical Society, 128(46), 14889-14896. https://doi.org/10.1021/ja064343u