Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion.
In this Article, we present a molecular-level understanding of the experimentally observed loss of crystallinity in UiO-66-type metal-organic frameworks, including the pristine UiO-66 to -68 as well as defect-containing UiO-66 materials, under the influence of external pressure. This goal is achieved by constructing pressure-versus-volume profiles at finite temperatures using a thermodynamic approach relying on ab initio derived force fields. On the atomic level, the phenomenon is reflected in a sudden drop in the number of symmetry operators for the crystallographic unit cell because of the disordered displacement of the organic linkers with respect to the inorganic bricks. For the defect-containing samples, a reduced mechanical stability is observed, however, critically depending on the distribution of these defects throughout the material, hence demonstrating the importance of judiciously characterizing defects in these materials.
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Sven M J
SM
Rogge
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Jelle
J
Wieme
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Louis
L
Vanduyfhuys
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Steven
S
Vandenbrande
Institut Charles Gerhardt Montpellier, Université Montpellier 2 , Place E. Bataillon, 34095 Montpellier cedex 05, France.
Guillaume
G
Maurin
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Toon
T
Verstraelen
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Michel
M
Waroquier
Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
Veronique
V
Van Speybroeck