期刊
AMERICAN MINERALOGIST
卷 97, 期 5-6, 页码 816-827出版社
MINERALOGICAL SOC AMER
DOI: 10.2138/am.2012.3903
关键词
XANES; valence determination; phyllomanganates; tectomanganates; manganese oxides
资金
- Office of Science, Office of Basic Energy Sciences, Materials Sciences Division of the U.S. Department of Energy at the Lawrence Berkeley National Laboratory [DE-AC02-05CH11231]
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.
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