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Electron transfer properties in the Prussian Blue analogues RbxMn[Fe(CN)6]y·zH2O

(2009) Vertelman, Esther Jacoba Martha

The research in this thesis was aimed at figuring out how the mechanism of the internal redox reaction in RbxMn[Fe(CN)6]y•zH2O exactly works. Also it was tried to fine tune the exact position and width of the temperature hysteresis. It turned out that the more [Fe(CN)6] defects are present in the final material, the less complete the internal redox reaction and the wider the hysteresis. This can be explained by a changed redox potential of the Mn ion which has, due to the defects, 5 cyanides and one water molecule rather than 6 cyanides. De most pronounced effect on the amount of defects is during the synthesis the addition speed of the manganese ion containing solution to the ironhexacyanide and rubidium containing solution. The slower this is, the better the Mn:Fe ratio: the system has enough time to replace the water molecules around manganese by the cyanides that are attached to iron. The percentage of material that shows an internal redox reaction is directly visible in the 57Fe Mössbauer spectrum at room temperature. Furthermore, for the first time it was possible to obtain single crystals that show an internal redoxreaction of 50% under the influence of temperature and light. The precize distribution of the rubidium ions and water molecules over the material is a possible explanation for the partial transfer rather than the expected complete transfer. Alkali ions other than rubidium turned out either not to be incorporated or the resulting material did not show an internal redox reaction.

	Title and contents
	Chapter 1
	Chapter 2
	Chapter 3
	Chapter 4
	Chapter 5
	Chapter 6
	Chapter 7
	Appendix I
	Appendix II
	Nederlandse samenvatting
	Dankwoord
	List of publications
	Complete thesis