期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 10, 期 6, 页码 1373-1382出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200305413
关键词
aluminum; breathing effects; dynamic frameworks hydrothermal synthesis; nanostructures; structure elucidation
Aluminum 1,4-benzenedicarboxylate Al(OH)[O2C-C6H4-CO2](.)[HO2C-C6H4-CO2H](0.70) or MIL-53 as (Al) has been hydrothermally synthesized by heating a mixture of aluminum nitrate, 1,4-benzenedicarboxylic acid, and water, for three days at 220degreesC. Its 3D framework is built up of infinite trans chains of corner-sharing AlO4(OH)(2) octahedra. The chains are interconnected by the 1,4-benzenedicarboxylate groups, creating ID rhombic-shaped tunnels. Disordered 1,4-benzenedicarboxylic acid molecules are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420degreesC. leads to a nanoporous open-framework (MIL-53ht (Al) or Al(OH)[O2C-C6H4-CO2]) with empty pores of diameter 8.5 Angstrom. This solid exhibits a Langmuir surface area of 1590(1) m(2)g(-1) together with a remarkable thermal stability, since it starts to decompose only at 500degreesC. At room temperature, the solid reversibly absorbs water in its tunnels, causing a very large breathing effect and shrinkage of the pores. Analysis of the hydration process by solid-state NMR (H-1, C-13, Al-27) has clearly indicated that the trapped water molecules interact with the carboxylate groups through hydrogen bonds, but do not affect the hydroxyl species bridging the aluminum atoms. ne hydrogen bonds between water and the oxygen atoms of the framework are responsible for the contraction of the rhombic channels. The structures of the three forms have been determined by means of powder X-ray diffraction analysis. Crystal data for MIL-53 as (Al) are as follows: orthorhombic system, Pnma (no. 62), a 17.129(2), b = 6.628(1), c = 12.182(1) A; for MIL-53ht (Al), orthorhombic system, Imma (no. 74), a = 6.608(1), b = 16.675(3), c = 12.813(2) Angstrom; for MIL-53 lt (Al), monoclinic system, Cc (no. 9), a = 19.513(2), b = 7.612(1), c = 6.576(1) Angstrom, beta = 104.24(1)degrees.
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