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Title: Understanding crystallization pathways leading to manganese oxide polymorph formation

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. In conclusion, our combined computational and experimental approach offers a rational and systematic paradigm for the aqueous synthesis of target metal oxides.
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  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. Colorado School of Mines, Golden, CO (United States)
  5. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 2041-1723
Grant/Contract Number:
AC36-08GO28308; AC02-05CH11231; AC02-76SF00515
Published Article
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Nature Publishing Group
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
36 MATERIALS SCIENCE; computational chemistry; materials chemistry; materials for energy and catalysis
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1461258; OSTI ID: 1462356