Cation Extraction Process in Bilayer Cyanide Film as Investigated by Depth-Resolved X-ray Absorption Spectroscopy

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The cation extraction process in the bilayer cyanide film with an epitaxial interface, Na0.84-yCo2+[FeyFe1-y(CN)6]0.713.8H2O (NCF71)/Na1.60-x(CoxCo1-x)[Fe2+(CN)6]0.902.8H2O (NCF90), was investigated by depth-resolved X-ray absorption spectroscopy. Assuming stepwise depth (z) distributions of Co3+ and Fe3+, we estimated the step depths, d_{\text{Co}} and d_{\text{Fe}}, and concentrations, \delta_{\text{Co}} and \delta_{\text{Fe}}, of the respective ions against the average quantity (\delta_{\text{av}}) of cation extraction. The Na+ extraction was found to be dominant in the NCF90 surface layer, consistent with the lower redox potential in the NCF90 layer. We found that the magnitude of d_{\text{Fe}} ({\sim}600 nm) is much deeper than the actual depth (d = 200 nm) of the NCF71/NCF90 interface, and interpreted the behavior in terms of the redox interaction in the vicinity of the interface.
2011-12-25