Spectroscopically Resolved Binding Sites for the Adsorption of Sarin Gas in a Metal-Organic Framework: Insights beyond Lewis Acidity.
J Phys Chem Lett
; 10(17): 5142-5147, 2019 Sep 05.
Article
em En
| MEDLINE
| ID: mdl-31402669
ABSTRACT
Here we report molecular level details regarding the adsorption of sarin (GB) gas in a prototypical zirconium-based metal-organic framework (MOF, UiO-66). By combining predictive modeling and experimental spectroscopic techniques, we unambiguously identify several unique bindings sites within the MOF, using the PâO stretch frequency of GB as a probe. Remarkable agreement between predicted and experimental IR spectrum is demonstrated. As previously hypothesized, the undercoordinated Lewis acid metal site is the most favorable binding site. Yet multiple sites participate in the adsorption process; specifically, the Zr-chelated hydroxyl groups form hydrogen bonds with the GB molecule, and GB weakly interacts with fully coordinated metals. Importantly, this work highlights that subtle orientational effects of bound GB are observable via shifts in characteristic vibrational modes; this finding has large implications for degradation rates and opens a new route for future materials design.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Tipo de estudo:
Prognostic_studies
Idioma:
En
Revista:
J Phys Chem Lett
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
Estados Unidos