Dynamic Interplay between Defective UiO-66 and Protic Solvents in Activated Processes |
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| Authors: | Chiara Caratelli Dr Ir Julianna Hajek Prof Dr Evert Jan Meijer Prof Dr Michel Waroquier Prof Dr Ir Veronique Van Speybroeck |
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| Institution: | 1. Center for Molecular Modeling, Ghent University, Technologiepark 46, 9052 Zwijnaarde, Belgium;2. Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands |
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| Abstract: | UiO-66, composed by Zr-oxide inorganic bricks Zr6(μ3-O)4(μ3-OH)4] and organic terephthalate linkers, is one of the most studied metal–organic frameworks (MOFs) due to its exceptional thermal, chemical, and mechanical stability. Thanks to its high connectivity, the material can withstand structural deformations during activation processes such as linker exchange, dehydration, and defect formation. These processes do alter the zirconium coordination number in a dynamic way, creating open metal sites for catalysis and thus are able to tune the catalytic properties. In this work, it is shown, by means of first-principle molecular-dynamics simulations at operating conditions, how protic solvents may facilitate such changes in the metal coordination. Solvent can induce structural rearrangements in the material that can lead to undercoordinated but also overcoordinated metal sites. This is demonstrated by simulating activation processes along well-chosen collective variables. Such enhanced MD simulations are able to track the intrinsic dynamics of the framework at realistic conditions. |
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| Keywords: | density functional calculations metal–organic frameworks molecular dynamics solvent UiO-66 |
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