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In situ Fe XAFS of reversible lithium insertion in a flexible metal organic framework material

By Guillaume de Combarieu, Stephane Hamelet, Franck Millange, Mathieu Morcrette, Jean-Marie Tarascon, Gerard Ferey and Richard I. Walton


X-ray absorption fine structure (XAFS) analysis of the Fe K-edge during lithium insertion and extraction into the metal organic framework material MIL-53 (Fe-III(OH, F)bdc; bdc = benzene-1,4-dicarboxylate) reveals changes in local atomic environment about iron during the process. The average oxidation state of iron is reduced upon lithium insertion, as evidenced by the edge shift of the XANES spectra, and this is accompanied by a lengthening of Fe-O bonds, seen in the EXAFS. In contrast, the EXAFS analysis shows that the closest Fe-Fe distance remains approximately constant during the insertion and extraction of lithium, consistent with a distortion of the structure due to its flexible nature. The process is reversible upon lithium extraction, proving the redox-active flexibility of the framework

Topics: QD
Publisher: Elsevier Inc.
Year: 2009
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