Understanding crystallization pathways leading to manganese oxide polymorph formation

Chen, Bor-Rong; Sun, Wenhao; Kitchaev, Daniil A.; Mangum, John S.; Thampy, Vivek; Garten, Lauren M.; Ginley, David S.; Gorman, Brian P.; Stone, Kevin H.; Ceder, Gerbrand; Toney, Michael F.; Schelhas, Laura T.

doi:10.1038/s41467-018-04917-y

Understanding crystallization pathways leading to manganese oxide polymorph formation

Journal Article · Fri Jun 29 00:00:00 EDT 2018 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-04917-y· OSTI ID:1457088

Chen, Bor-Rong; Sun, Wenhao; ; Mangum, John S.; Thampy, Vivek; Garten, Lauren M.; Ginley, David S.; Gorman, Brian P.; ; Ceder, Gerbrand; ;

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 MnO ₂ 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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1457088

Alternate ID(s):: OSTI ID: 1506381
OSTI ID: 1461258
OSTI ID: 1462356

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 9; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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