NMR Spectroscopy Reveals Adsorbate Binding Sites in the Metal–Organic Framework UiO-66(Zr)
| Autor: | Jeffrey A. Reimer, Aditya Nandy, Alexander C. Forse, Velencia J. Witherspoon |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Cyclohexane
Chemistry Chemical shift 02 engineering and technology Nuclear magnetic resonance spectroscopy Carbon-13 NMR 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Crystallography chemistry.chemical_compound General Energy Adsorption Cluster (physics) Metal-organic framework Density functional theory Physical and Theoretical Chemistry 0210 nano-technology |
| Zdroj: | The Journal of Physical Chemistry C. 122:8295-8305 |
| ISSN: | 1932-7455 1932-7447 |
| Popis: | We assign 1H and 13C NMR resonances emanating from acetone, methanol, and cyclohexane adsorbed inside the pores of UiO-66(Zr). These results are informed by density functional theory (DFT) calculations, which probe the role of two competing effects inside of the pore environment: (i) nucleus independent chemical shifts (NICSs) generated by ring currents in conjugated linkers and (ii) small molecule coordination to the metal-oxyhydroxy cluster. These interactions are found to perturb the chemical shift of in-pore adsorbate relative to ex-pore adsorbate (which resides in spaces between the MOF particles). Changes in self-solvation upon adsorption may also perturb the chemical shift. Our results indicate that cyclohexane preferentially adsorbs in the tetrahedral pores of UiO-66(Zr), while acetone and methanol adsorb at the Zr–OH moieties on the metal-oxyhydroxy clusters in a more complex fashion. This method may be used to probe molecular adsorption sites and material void saturation with selected adsorbates... |
| Databáze: | OpenAIRE |
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