Abstract
Potassium cobalt hexacyanoferrate(II) [K2CoFe(CN)6] is an extremely selective ion exchanger for cesium ions. To examine the atomic level background for the selectivity a computational structural study using DFT modelling was carried out for K2CoFe(CN)6 and for products where Cs has replaced K in the elemental cube cages closest to the surface. In the K-form compound the potassium ions are not in the center of the Co–Fe–CN elementary cube cages closest to the surface but locate about 140 pm from the cube center towards the surface. When cesium ions are exchanged to these potassium ions they locate much deeper from the surface, being only about 70 pm upwards from the cube center. This apparently leads to much stronger bonding of cesium compared to potassium. Once taken up into the outermost cube cages on the surface of the crystallites cesium ions are not able to penetrate further since they are much larger than the electron window between the cubes. Furthermore, they are not able to return to the solution phase either leading to a practically irreversible sorption.
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