Selective Synthesis of Defect-Rich LaMnO₃ by Low-Temperature Anion Cometathesis

The synthesis of complex oxides at low temperatures brings forward aspects of chemistry not typically considered. This study focuses on perovskite LaMnO₃, which is of interest for its correlated electronic behavior tied to the oxidation state and thus the spin configuration of manganese. Traditional equilibrium synthesis of these materials typically requires synthesis reaction temperatures in excess of 1000 °C, followed by subsequent annealing steps at lower temperatures and different <i>p</i>(O₂) conditions to manipulate the oxygen content postsynthesis (e.g., LaMnO_3+<i>x</i>). Double-ion exchange (metathesis) reactions have recently been shown to react at much lower temperatures (500-800 °C), highlighting a fundamental knowledge gap for how solids react at lower temperatures. Here, we revisit the metathesis reaction, LiMnO₂ + LaOX, where X is a halide or mixture of halides, using in situ synchrotron X-ray diffraction. These experiments reveal low reaction onset temperatures (ca. 450-480 °C). The lowest reaction temperatures are achieved by a mixture of lanthanum oxyhalide precursors: 2 LiMnO₂ + LaOCl + LaOBr. In all cases, the resulting products are the expected alkali halide salt and defective La_1-ϵMn_1-ϵO₃, where ϵ = <i>x</i>/(3 + <i>x</i>). We observe a systematic variation in defect concentration, consistent with a rapid stoichiometric local equilibration of the precursors and the subsequent global thermodynamic equilibration with O₂ (g), as revealed by computational thermodynamics. Together, these results reveal how the inclusion of additional elements (e.g., Li and a halide) leads to the local equilibrium, particularly at low reaction temperatures for solid-state chemistry.