Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

Inorg Chem. 2020 Sep 21;59(18):13639-13650. doi: 10.1021/acs.inorgchem.0c02023. Epub 2020 Aug 31.

ABSTRACT

In the synthesis of complex oxides, solid-state metathesis provides low-temperature reactions where product selectivity can be achieved through simple changes in precursor composition. The influence of precursor structure, however, is less understood in solid-state synthesis. Here we present the ternary metathesis reaction (LiMnO₂ + YOCl → YMnO₃ + LiCl) to target two yttrium manganese oxide products, hexagonal and orthorhombic YMnO₃, when starting from three different LiMnO₂ precursors. Using temperature-dependent synchrotron X-ray and neutron diffraction, we identify the relevant intermediates and temperature regimes of reactions along the pathway to YMnO₃. Manganese-containing intermediates undergo a charge disproportionation into a reduced Mn(II,III) tetragonal spinel and oxidized Mn(III,IV) cubic spinel, which lead to hexagonal and orthorhombic YMnO₃, respectively. Density functional theory calculations confirm that the presence of Mn(IV) caused by a small concentration of cation vacancies (∼2.2%) in YMnO₃ stabilizes the orthorhombic polymorph over the hexagonal. Reactions over the course of 2 weeks yield o-YMnO₃ as the majority product at temperatures below 600 °C, which supports an equilibration of cation defects over time. Controlling the composition and structure of these defect-accommodating intermediates provides new strategies for selective synthesis of complex oxides at low temperatures.

PMID:32866379 | DOI:10.1021/acs.inorgchem.0c02023