Journal ArticleDOI
A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL‐53) Upon Hydration
Thierry Loiseau,Christian Serre,Clarisse Huguenard,Gerhard Fink,Francis Taulelle,Marc Henry,Thierry Bataille,Gérard Férey,Gérard Férey +8 more
TLDR
Analysis of the hydration process by solid-state NMR 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.Abstract:
Aluminum 1,4-benzenedicarboxylate Al(OH)[O2CC6H4CO2]⋅ [HO2CC6H4CO2H]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)[O2CC6H4CO2]) with empty pores of diameter 8.5 A. 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) A; for MIL-53 ht (Al), orthorhombic system, Imma (no. 74), a = 6.608(1), b = 16.675(3), c = 12.813(2) A; for MIL-53 lt (Al), monoclinic system, Cc (no. 9), a = 19.513(2), b = 7.612(1), c = 6.576(1) A, β = 104.24(1)°.read more
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Metal–Organic Frameworks for Separations
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Carbon Dioxide Capture in Metal–Organic Frameworks
Kenji Sumida,David L. Rogow,Jarad A. Mason,Thomas M. McDonald,Eric D. Bloch,Zoey R. Herm,Tae-Hyun Bae,Jeffrey R. Long +7 more
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A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability.
Jasmina Hafizovic Cavka,Søren Jakobsen,Unni Olsbye,Nathalie Guillou,Carlo Lamberti,Silvia Bordiga,Karl Petter Lillerud +6 more
TL;DR: The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.