Abstract
Nanoparticles are ubiquitous in both natural and synthetic environments, providing much of the chemical reactivity for geochemical, planetary, environmental, and technological processes. However, this reactivity and differences between the bulk and nanoscale are thermodynamically, as well as kinetically, controlled. Energetic effects arising from differences in surface energies of different nanomaterials lead to changes in which phases are thermodynamically stable under given conditions. This results in crossovers in polymorphic stability as a function of particle size and substantial shifts in the positions of dehydration and redox equilibria. Examples of these phenomena in aluminum, cobalt, iron, and manganese oxides are presented, and implications for catalysts, battery materials, and other functional oxides are discussed. A hypothesis is presented that low surface energy and the resulting relatively weak water binding on the surface leads to better function when electrons or ions are transferred at the solid-solution interface.
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Acknowledgments
I thank the many students and postdocs who have worked with me on these projects, the many colleagues who have encouraged me and provided spirited discussions and constructive criticism, and the National Science Foundation and US Department of Energy for almost continuous support of this line of research from both the geochemical and materials point of view.
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The following article is based on a Symposium X (Frontiers of Materials Research) presentation given by Alexandra Navrotsky at the 2015 MRS Spring Meeting in San Francisco.
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Navrotsky, A. Energetics at the nanoscale: Impacts for geochemistry, the environment, and materials. MRS Bulletin 41, 139–145 (2016). https://doi.org/10.1557/mrs.2015.336
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DOI: https://doi.org/10.1557/mrs.2015.336