Study of mixed-valence Mn2BO4 using XRD, XPS and XAFS spectroscopies

The valence states and local structure around Mn atoms in mixed-valence Mn2BO4 have been studied by temperature dependent X-ray powder diffraction (XRPD), X-ray photoelectron (XPS) and Mn K-edge X-ray absorption (XAFS) spectroscopies measurements. X-ray absorption near-edge structure (XANES) and XPS have been used to measure the average oxidation state of Mn in bulk and near-surface of the material. The edge position, peak shapes and pre-edge features of Mn K-edge XANES spectra have been discussed. The pronounced temperature dependence of the Debye-Waller (DW) factor corresponding to the MnO coordination shell has been found from the extended x-ray absorption fine structure (EXAFS) analysis and has been associated with variations in the local distortions in MnO6 octahedra and emergence of short-range magnetic correlations at low temperatures. The XRPD measurements have been carried out at 298, 523 and 773 K. The monoclinic symmetry (P21/n) was found to persist up to highest temperature measured. The BVS calculations have revealed large valence difference between two manganese sites that strongly supports the presence of charge ordering up to high temperatures. •The monoclinic symmetry was found to persist up to 973 K.•The large bond-valence difference between Mn1 and Mn2 sites suggests the presence of the charge ordering up to highest temperature measured.•The DW factor is progressively reduced below 100 K and goes through a minimum at the TN.•The average manganese oxidation state in bulk was found to be Mn(2.55±0.08)+.