Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy
-
Alain Manceau
,
Matthew A. Marcus
Abstract
The valence states of Mn in mixed-valent layer and tunnel structure manganese dioxides (MnO2), usually referred to as phyllomanganates and tectomanganates, can be measured by X-ray absorption near-edge structure (XANES) spectroscopy with a precision and accuracy that are difficult to estimate owing to the paucity of well-characterized standards. A compilation of the Mn K-edge XANES spectra of most naturally occurring manganates, synthetic analogs of known structure and chemical composition, and pure-valence phase species is presented and made available as an open source. We intend this compilation to serve as a basis for the spectroscopic determination of the fractions of the Mn 2+, 3+, and 4+ valences in mixed-valent manganates and phase mixtures. The XANES derivatives of tectomanganates and phyllomanganates with no or little Mn3+ in the MnO2 layer exhibit intensities, shapes, and relative energy positions of the main features characteristics of a particular valence composition. For these compounds, valence fractions can be derived using linear combination fitting analysis. Best quantitative results are obtained when the unknown spectrum is fit to a weighted sum of all reference spectra in the database with the fractions of species constrained to be non-negative (Combo method). The accuracy of the average valence is estimated to 0.04 v.u. in the range of 3+ to 4+, and decreases when the proportion of divalent Mn is higher than 15%. The accuracy of the method is also lower in (layer Mn3+, Mn4+) manganates, because the XANES features are affected non-additively by the amount and distribution of the Jahn-Teller Mn3+ cations. The merit of the Combo method for the determination of manganese valence sums relative to the methods based on calibration curves is discussed.
© 2015 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- Dana medal lecture: Tilts and tetrahedra: The origin of the anisotropy of feldspars
- Amorphous Materials: Determination of water content in silicate glasses using Raman spectrometry: Implications for the study of explosive volcanism
- Density functional calculations of the enthalpies of formation of rare-earth orthophosphates
- U-Pb ID-TIMS dating applied to U-rich inclusions in garnet
- Wassonite: A new titanium monosulfide mineral in the Yamato 691 enstatite chondrite
- Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy
- The morphology of the reaction front of the dissolutionprecipitation reaction rutile + wollastonite = titanite in time series experiments at 600 °C/400 MPa
- Precipitation of rutile and ilmenite needles in garnet: Implications for extreme metamorphic conditions in the Acadian Orogen, U.S.A.
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- Investigation of cation ordering in triclinic sodium birnessite via 23Na MAS NMR spectroscopy
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- Pressure-induced changes in local electronic structures of SiO2 and MgSiO3 polymorphs: Insights from ab initio calculations of O K-edge energy-loss near-edge structure spectroscopy
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- Characterization of smectite to NH4-illite conversion series in the fossil hydrothermal system of Harghita Bãi, East Carpathians, Romania
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