Dynamic interplay between defective UiO‐66 and protic solvents in activated processes
| Autor: | Michel Waroquier, Evert Jan Meijer, Julianna Hajek, Veronique Van Speybroeck, Chiara Caratelli |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
INITIO MOLECULAR-DYNAMICS
Coordination number NANOTUBES chemistry.chemical_element 010402 general chemistry 01 natural sciences solvent Catalysis Metal–Organic Frameworks Metal Molecular dynamics METAL-ORGANIC FRAMEWORKS WATER Reactivity (chemistry) EXCHANGE Zirconium SITES Full Paper 010405 organic chemistry TOTAL-ENERGY CALCULATIONS POSTSYNTHETIC LIGAND Organic Chemistry General Chemistry Full Papers molecular dynamics REACTIVITY 0104 chemical sciences Solvent Chemistry chemistry Physics and Astronomy Chemical physics UiO-66 visual_art density functional calculations visual_art.visual_art_medium Metal-organic framework |
| Zdroj: | CHEMISTRY-A EUROPEAN JOURNAL Chemistry (Weinheim an Der Bergstrasse, Germany) Chemistry – A European Journal |
| ISSN: | 0947-6539 1521-3765 |
| Popis: | 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. Bricks and linkers: The UiO‐66 MOF, although very robust, shows an exceptionally dynamic behavior of linkers in presence of a solvent. In this contribution simulations at operating conditions are used to track at the molecular level how solvent triggers processes such as linker exchange and defect formation in the material. |
| Databáze: | OpenAIRE |
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