Skip to main content
eScholarship
Open Access Publications from the University of California

Understanding crystallization pathways leading to manganese oxide polymorph formation

  • Author(s): Chen, BR
  • Sun, W
  • Kitchaev, DA
  • Mangum, JS
  • Thampy, V
  • Garten, LM
  • Ginley, DS
  • Gorman, BP
  • Stone, KH
  • Ceder, G
  • Toney, MF
  • Schelhas, LT
  • et al.
Abstract

© 2018 The Author(s). Hydrothermal synthesis is challenging in metal oxide systems with diverse polymorphism, as reaction products are often sensitive to subtle variations in synthesis parameters. This sensitivity is rooted in the non-equilibrium nature of low-Temperature crystallization, where competition between different metastable phases can lead to complex multistage crystallization pathways. Here, we propose an ab initio framework to predict how particle size and solution composition influence polymorph stability during nucleation and growth. We validate this framework using in situ X-ray scattering, by monitoring how the hydrothermal synthesis of MnO2proceeds through different crystallization pathways under varying solution potassium ion concentrations ([K+] = 0, 0.2, and 0.33 M). We find that our computed size-dependent phase diagrams qualitatively capture which metastable polymorphs appear, the order of their appearance, and their relative lifetimes. Our combined computational and experimental approach offers a rational and systematic paradigm for the aqueous synthesis of target metal oxides.

Many UC-authored scholarly publications are freely available on this site because of the UC Academic Senate's Open Access Policy. Let us know how this access is important for you.

Main Content
Current View