Understanding crystallization pathways leading to manganese oxide polymorph formation

Bor-Rong Chen, Wenhao Sun, Daniil A. Kitchaev, John S. Mangum, Vivek Thampy, Lauren M. Garten, David S. Ginley, Brian P. Gorman, Kevin H. Stone, Gerbrand Ceder (), Michael F. Toney () and Laura T. Schelhas ()
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Bor-Rong Chen: SLAC National Accelerator Laboratory
Wenhao Sun: Lawrence Berkeley National Laboratory
Daniil A. Kitchaev: Massachusetts Institute of Technology
John S. Mangum: Colorado School of Mines
Vivek Thampy: SLAC National Accelerator Laboratory
Lauren M. Garten: National Renewable Energy Laboratory
David S. Ginley: National Renewable Energy Laboratory
Brian P. Gorman: Colorado School of Mines
Kevin H. Stone: SLAC National Accelerator Laboratory
Gerbrand Ceder: Lawrence Berkeley National Laboratory
Michael F. Toney: SLAC National Accelerator Laboratory
Laura T. Schelhas: SLAC National Accelerator Laboratory

Nature Communications, 2018, vol. 9, issue 1, 1-9

Abstract: Abstract 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 MnO2 proceeds 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.

Date: 2018
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DOI: 10.1038/s41467-018-04917-y

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