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Dissolution of insulating oxide materials at the molecular scale

Nature Materials volume 9, pages 11–19 (2010)Cite this article

Abstract

Our understanding of mineral and glass dissolution has advanced from simple thermodynamic treatments to models that emphasize adsorbate structures. This evolution was driven by the idea that the best understanding is built at the molecular level. Now, it is clear that the molecular questions cannot be answered uniquely with dissolution experiments. At the surface it is unclear which functional groups are present, how they are arranged, and how they interact with each other and with solutes as the key bonds are activated. An alternative approach has developed whereby reactions are studied with nanometre-sized aqueous oxide ions that serve as models for the more complicated oxide interface. For these ions, establishing the structure is not a research problem in itself, and bond ruptures and dissociations can be followed with much confidence. We review the field from bulk-dissolution kinetics to the new isotope-exchange experiments in large oxide ions.

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Figure 1: Dissolution kinetics.
Figure 2: Rapid oxygen-isotope scrambling on the (012) surface of α-Fe2 18O3 following deposition of H2 16O.
Figure 3: The replacement of a metal-bound water with one from the bulk is the most fundamental interfacial reaction in aqueous solutions.
Figure 4: Oxygen-isotope-exchange pathways in [MO4Al12(OH)24(H2O)12]7/8+ cations (M = Al, Ga and Ge).
Figure 5: Oxygen-isotope-exchange pathways in the nanometre-sized decaniobate ([HxNb10O28](6−x)−) anion.
Figure 6: Pathways for isotope exchanges can be grouped into three related classes.

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Acknowledgements

Support for this research came from the National Science Foundation via grant EAR 05015600 and from the US Department of Energy Office of Basic Energy Science via grant numbers DE-FG03-96ER 14629 and DE-FG03-02ER15693. Special thanks also goes to Phil Power who encouraged us to propose this article.

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  1. Department of Chemistry, University of California, Davis, 95616, California, USA

    C. André Ohlin, Eric M. Villa & William H. Casey

  2. Department of Geology, University of California, Davis, 95616, California, USA

    C. André Ohlin, Eric M. Villa, James R. Rustad & William H. Casey

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Ohlin, C., Villa, E., Rustad, J. et al. Dissolution of insulating oxide materials at the molecular scale. Nature Mater 9, 11–19 (2010). https://doi.org/10.1038/nmat2585

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