Article ID Journal Published Year Pages File Type
1237080 Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2009 9 Pages PDF
Abstract
A detailed comparison has been made of determinations by 57Fe Mössbauer spectroscopy and four different XAFS spectroscopic methods of %Fe as hematite and ferrihydrite in 11 iron-based SBA-15 catalyst formulations. The four XAFS methods consisted of least-squares fitting of iron XANES, d(XANES)/dE, and EXAFS (k3chi and k2chi) spectra to the corresponding standard spectra of hematite and ferrihydrite. The comparison showed that, for this particular application, the EXAFS methods were superior to the XANES methods in reproducing the results of the benchmark Mössbauer method in large part because the EXAFS spectra of the two iron-oxide standards were much less correlated than the corresponding XANES spectra. Furthermore, the EXAFS and Mössbauer results could be made completely consistent by inclusion of a factor of 1.3 ± 0.05 for the ratio of the Mössbauer recoilless fraction of hematite relative to that of ferrihydrite at room temperature (293 K). This difference in recoilless fraction is attributed to the nanoparticle nature of the ferrihydrite compared to the bulk nature of the hematite. Also discussed are possible alternative non-least-squares XAFS methods for determining the iron speciation in this application as well as criteria for deciding whether or not least-squares XANES methods should be applied for the determination of element speciation in unknown materials.
Related Topics
Physical Sciences and Engineering Chemistry Analytical Chemistry
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