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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate
Published on: February 23, 2016
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Aqueous tantalum polyoxometalate reactivity with peroxide
Lauren B Fullmer1, Christopher E Malmberg, Dylan B Fast
1Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97333, USA. may.nyman@science.oreongstate.edu.
Dalton Transactions (Cambridge, England : 2003)
|June 21, 2017
Summary
Peroxide ligation of polyoxotantalate clusters links them together in solution, unlike their niobate counterparts. This finding is key for developing new tantalum-based materials and solution-processed thin films.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Peroxide ligation of metal-oxo clusters offers diverse speciation, structural variety, and tunable stability.
- Polyoxometalates (POMs) are versatile inorganic clusters with applications in catalysis and materials science.
Purpose of the Study:
- To investigate the solution speciation of peroxide-ligated polyoxotantalate clusters ([Ta6O19]8-).
- To compare the behavior of peroxide-ligated tantalates with their niobate analogues.
- To understand the structural implications of peroxide ligation in POMs for materials applications.
Main Methods:
- Raman spectroscopy
- Electrospray ionization mass spectrometry (ESI-MS)
- Small, wide-angle, and total X-ray scattering (SAXS/WAXS/TXS)
- Computational studies (DFT)
Main Results:
- Raman and ESI-MS showed no significant differences between peroxide-ligated tantalate and niobate clusters.
- X-ray scattering data indicated that peroxide ligation promotes linking of tantalate clusters, contrasting with capping observed in niobates.
- Computational studies elucidated Raman spectra, ligand exchange energetics, and provided models for X-ray scattering observations.
Conclusions:
- Peroxide ligation induces distinct solution-phase structural behavior in polyoxotantalates compared to polyoxoniobates.
- Understanding this solution speciation is crucial for advancing tantalum-based POM chemistry and solution-processed thin film materials.
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