Selectivity in Yttrium Manganese Oxide Synthesis via Local Chemical Potentials in Hyperdimensional Phase Space

Todd, Paul K.; McDermott, Matthew J.; Rom, Christopher L.; Corrao, Adam A.; Denney, Jonathan J.; Dwaraknath, Shyam S.; Khalifah, Peter G.; Persson, Kristin A.; Neilson, James R.

doi:10.1021/jacs.1c06229

Title: Selectivity in Yttrium Manganese Oxide Synthesis via Local Chemical Potentials in Hyperdimensional Phase Space

Journal Article · 07 September 2021 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.1c06229 · OSTI ID:1818916

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Colorado State Univ., Fort Collins, CO (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Stony Brook Univ., NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

In sharp contrast to molecular synthesis, materials synthesis is generally presumed to lack selectivity. The few known methods of designing selectivity in solid-state reactions have limited scope, such as topotactic reactions or strain stabilization. This contribution describes a general approach for searching large chemical spaces to identify selective reactions. This novel approach explains the ability of a nominally “innocent” Na₂CO₃ precursor to enable the metathesis synthesis of single-phase Y₂Mn₂O₇: an outcome that was previously only accomplished at extreme pressures and which cannot be achieved with closely related precursors of Li₂CO₃ and K₂CO₃ under identical conditions. By calculating the required change in chemical potential across all possible reactant-product interfaces in an expanded chemical space including Y, Mn, O, alkali metals, and halogens, using thermodynamic parameters obtained from density functional theory calculations, we identify reactions that minimize the thermodynamic competition from intermediates. In this manner, only the Na-based intermediates minimize the distance in the hyperdimensional chemical potential space to Y₂Mn₂O₇, thus providing selective access to a phase which was previously thought to be metastable. Experimental evidence validating this mechanism for pathway-dependent selectivity is provided by intermediates identified from in situ synchrotron-based crystallographic analysis. Finally, this approach of calculating chemical potential distances in hyperdimensional compositional spaces provides a general method for designing selective solid-state syntheses that will be useful for gaining access to metastable phases and for identifying reaction pathways that can reduce the synthesis temperature, and cost, of technological materials.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1818916

Report Number(s):: BNL--222073-2021-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 37 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical reactions
Metathesis
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Transition metals

Title: Selectivity in Yttrium Manganese Oxide Synthesis via Local Chemical Potentials in Hyperdimensional Phase Space

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