RESUMO
α-MnO2 nanorods were synthesized via the hydrothermal decomposition of KMnO4 in an acidic environment in the presence of Co2+ and Cr3+ ions. Reactions were carried out at three different temperatures: 90, 130 and 170 °C. All prepared samples exhibit a tetragonal MnO2 crystalline phase. SEM-EDS analysis shows that cobalt cations are incorporated to a higher degree into the MnO2 framework than chromium ions, and that the content of the dopant ions decreases with increasing reaction temperature. The oxidation of Co2+ to Co3+ during the reaction was proved by an XANES study, while EXAFS results confirm that both dopant ions substitute Mn4+ in the center of an octahedron. The K/Mn ratio in the doped samples synthesized at 170 °C is significantly lower than in the undoped samples. Analysis of an individual cobalt-doped α-MnO2 nanorod with HAADF-STEM reveals that the distribution of cobalt through the cross-section of the nanorod is uniform. The course of thermal decomposition of the doped nanorods is similar to that of the undoped ones. Dopant ions do not preserve the MnO2 phase at higher temperatures nor do they destabilize the cryptomelane structure.
RESUMO
The approximate barium X-ray atomic absorption in the energy region of L-edges is reconstructed from the absorption spectrum of an aqueous solution of BaCl(2). The result is corroborated by comparison with pure atomic absorption spectra of neighbour elements Xe and Cs. The application of the atomic absorption signal as a proper EXAFS background is demonstrated and discussed in the analysis of Ba hexaferrite nanoparticles with a very weak structural signal. The essential gain is found in the decrease of uncertainty intervals of structural parameters and their correlations. A simple analytical model of the absorption background for the practical EXAFS analysis is demonstrated.
