Non-equilibrium crystallization pathways of manganese oxides in aqueous solution
Publication date
2019
Document type
Research article
Author
Organisational unit
Engineering Sciences, University of Southampton, Southampton, SO17 1BJ, UK
ISSN
Series or journal
Nature Communications
Periodical volume
10
First page
1
Last page
9
Peer-reviewed
✅
Part of the university bibliography
Nein
Abstract
Aqueous precipitation of transition metal oxides often 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. Here, 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.
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