DOI: 10.1002/chem.200305413. A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL‐53) Upon Hydration

A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL‐53) Upon Hydration

10.1002/chem.200305413

Crossref journal-article

Wiley

Chemistry – A European Journal (311)

Abstract

AbstractAluminum 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 220 °C. Its 3 D 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 1 D rhombic‐shaped tunnels. Disordered 1,4‐benzenedicarboxylic acid molecules are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420 °C, leads to a nanoporous open‐framework (MIL‐53 ht (Al) or Al(OH)[O2CC6H4CO2]) with empty pores of diameter 8.5 Å. This solid exhibits a Langmuir surface area of 1590(1) m2 g−1 together with a remarkable thermal stability, since it starts to decompose only at 500 °C. 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 (1H, 13C, 27Al) 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. The 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) Å; for MIL‐53 ht (Al), orthorhombic system, Imma (no. 74), a = 6.608(1), b = 16.675(3), c = 12.813(2) Å; for MIL‐53 lt (Al), monoclinic system, Cc (no. 9), a = 19.513(2), b = 7.612(1), c = 6.576(1) Å, β = 104.24(1)°.

Bibliography

Loiseau, T., Serre, C., Huguenard, C., Fink, G., Taulelle, F., Henry, M., Bataille, T., & FÃ©rey, G. (2004). A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MILâ53) Upon Hydration. Chemistry â A European Journal, 10(6), 1373â1382. Portico.

Authors 8

Thierry Loiseau (first)
Christian Serre (additional)
Clarisse Huguenard (additional)
Gerhard Fink (additional)
Francis Taulelle (additional)
Marc Henry (additional)
Thierry Bataille (additional)
Gérard Férey (additional)

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Dates

Type	When
Created	21 years, 5 months ago (March 19, 2004, 10:59 a.m.)
Deposited	1 year, 10 months ago (Oct. 11, 2023, 6:56 p.m.)
Indexed	2 hours, 32 minutes ago (Aug. 21, 2025, 1:51 p.m.)
Issued	21 years, 5 months ago (March 15, 2004)
Published	21 years, 5 months ago (March 15, 2004)
Published Online	21 years, 5 months ago (March 15, 2004)
Published Print	21 years, 5 months ago (March 19, 2004)

Funders 0

None

BibTeX

@article{Loiseau_2004, title={A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL‐53) Upon Hydration}, volume={10}, ISSN={1521-3765}, url={http://dx.doi.org/10.1002/chem.200305413}, DOI={10.1002/chem.200305413}, number={6}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Loiseau, Thierry and Serre, Christian and Huguenard, Clarisse and Fink, Gerhard and Taulelle, Francis and Henry, Marc and Bataille, Thierry and Férey, Gérard}, year={2004}, month=mar, pages={1373–1382} }

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