Manganese oxides synthesized via microwave-assisted hydrothermal method: phase evolution and structure refinement

Manganese oxides were synthesized during 40 min at 140 degrees C via Microwave-Assisted Hydrothermal (MAH) method and treated at different temperatures in order to evaluate the phase evolution using structure refinement (Rietveld method). The samples obtained were heat treated at temperatures defined by means of thermal analysis (160 degrees C, 480 degrees C, 715 degrees C, 870 degrees C, 920 degrees C and 1150 degrees C) and analyzed by X-Ray Diffractometry (XRD), X-Ray Fluorescence (XRF), Fourier Transform Infrared (FTIR) spectroscopy, Raman scattering, UV-Vis absorption and Scanning Electron Microscopy (SEM). Structural characterizations allowed to identify five distinct phases: alpha-MnO2, Mn3O4, Mn5O8, Na2Mn5O10 and Na4Mn9O18 with weight percentages dependent on the heat treatment. The hausmannite structure (average crystallite size ranging from 28.9 nm to 99.1 nm) is present in all samples and go through various oxidation and reduction processes from 160 degrees C to 1150 degrees C without any major variation in the lattice parameters. Chemical characterizations identifies the presence of Na+ ions in all samples, either as substitution defects or as components of specific crystalline structures (Na2Mn5O10 and Na4Mn9O18), showing that the synthesized manganese oxides works as Na+ intercalation compounds, important materials for energy storage devices optimization. The results presented enables a better interpretation of the thermal and structural characteristics of manganese oxides synthesized via MAH.