Non-equilibrium crystallization pathways of manganese oxides in aqueous solution

Sun, Wenhao; Kitchaev, Daniil A.; Kramer, Denis; Ceder, Gerbrand

doi:10.1038/s41467-019-08494-6

Non-equilibrium crystallization pathways of manganese oxides in aqueous solution

Journal Article · Sun Feb 03 23:00:00 EST 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-08494-6· OSTI ID:1542369

Sun, Wenhao ^[1]; ^[2]; ^[3]; Ceder, Gerbrand ^[4]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Univ. of Southampton (United Kingdom)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Aqueous precipitation of transition metal oxides normally proceeds through non-equilibrium phases, whose appearance cannot be anticipated from traditional phase diagrams. Without a precise understanding of which metastable phases form, or their lifetimes, targeted synthesis of specific metal oxides can become a trial-and-error process. In this work, we construct a theoretical framework to reveal the nanoscale and metastable energy landscapes of Pourbaix (E-pH) diagrams, providing quantitative insights into the size-dependent thermodynamics of metastable oxide nucleation and growth in water. By combining this framework with classical nucleation theory, we interrogate how solution conditions influence the multistage oxidation pathways of manganese oxides. We calculate that even within the same stability region of a Pourbaix diagram, subtle variations in pH and redox potential can redirect a non-equilibrium crystallization pathway through different metastable intermediates. Our theoretical framework offers a predictive platform to navigate through the thermodynamic and kinetic energy landscape towards the rational synthesis of target materials.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1542369

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 10; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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