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Coordinative interaction between nitrogen oxides and iron-molybdenum POM Mo72Fe30
Kirill V Grzhegorzhevskii1, Margarita O Tonkushina, Andrei V Fokin
1Institute of Natural Sciences and Mathematics, Ural Federal University named after the B.N. Yeltsin, 620002, Ekaterinburg, Russia. kirillvalentinovich@urfu.ru.
Dalton Transactions (Cambridge, England : 2003)
|May 3, 2019
Summary
Giant Keplerate nanoclusters Mo72Fe30 effectively adsorb nitrogen oxides (NOx) under ambient conditions. This adsorption forms nitrate ions and a novel complex, [POM-(NO2)x]·(NO2)y, with potential biomedical applications as a NOx donor.
Area of Science:
- Nanomaterials Chemistry
- Inorganic Chemistry
- Surface Science
Background:
- Giant Keplerate nanoclusters, specifically Mo72Fe30, are complex inorganic structures.
- Understanding the interaction of nanoclusters with environmental gases like nitrogen oxides (NOx) is crucial.
Purpose of the Study:
- To investigate the adsorption mechanism of nitrogen monoxide (NO) and nitrogen dioxide (NO2) on the Mo72Fe30 nanocluster.
- To characterize the resulting complex and evaluate its properties for potential applications.
Main Methods:
- Raman and Infrared (IR) spectroscopy to identify chemical changes.
- Elemental analysis and X-ray photoelectron spectroscopy (XPS) for composition determination.
- Thermal analysis (TGA/DSC) and Electron Paramagnetic Resonance (EPR) spectroscopy to study thermal stability and molecular behavior.
Main Results:
- Adsorption of NOx leads to the formation of nitrate ions through oxygen sharing with FeO6 polyhedra.
- The complex formed has the composition [POM-(NO2)x]·(NO2)y (x=6, y=14±3).
- NOx coordination influences water release and acetate ligand decomposition; NO2 molecules delocalize at 25°C and localize at cryogenic temperatures, distorting FeO6 octahedra.
Conclusions:
- Mo72Fe30 nanoclusters effectively adsorb NOx, forming stable nitrate complexes.
- The resulting complex exhibits properties like high NO2 capacity, water solubility, and pH-dependent decomposition.
- These characteristics suggest potential applications as a NOx donor in biomedicine.
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