The relationship between Mn oxidation state and structure in triclinic and hexagonal birnessites

We explored these issues by synthesizing a host of cation-exchanged birnessite specimens whose long-range symmetrical character could be determined by X-ray diffraction without ambiguity. Through a combination of Fourier transform infrared spectroscopy (FTIR), extended X-ray absorption fine structure (EXAFS), and X-ray photoelectron spectroscopy (XPS), we have examined the relationships among structural symmetry, Mn oxidation state, and interlayer composition. Our results confirm prior models that as the concentration of Mn3+ increases, the departure from hexagonal symmetry also increases. Rietveld refinements indicate that the Jahn-Teller distortions associated with Mn3+ induce systematic variations in unit-cell parameters, particularly an increase in the a-axis and the β angle of the unit cell. Interlayer cation composition also controls structural distortions, and Ca-rich birnessites showed less deviation from hexagonality than did Na-, K-, and Ba-birnessites. Our linear combination fits of X-ray absorption spectra sometimes yielded misleading results, reinforcing the difficulty and importance of selecting appropriate standards.