TY - JOUR
T1 - Synthesis of MIL-102, a chromium carboxylate metal-organic framework, with gas sorption analysis
AU - Surblé, Suzy
AU - Millange, Franck
AU - Serre, Christian
AU - Düren, Tina
AU - Latroche, Michel
AU - Bourrelly, Sandrine
AU - Llewellyn, Philip L.
AU - Férey, Gérard
PY - 2006/11/22
Y1 - 2006/11/22
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=33845224297&partnerID=8YFLogxK
U2 - 10.1021/ja064343u
DO - 10.1021/ja064343u
M3 - Article
AN - SCOPUS:33845224297
SN - 0002-7863
VL - 128
SP - 14889
EP - 14896
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 46
ER -