Distinct ionic adsorption sites in defective Prussian blue: a 3D-RISM study

Abstract

Ferric hexacyanoferrate (FeHCF) or Prussian blue (PB) exhibits selective alkali ion adsorption and has great potential for use in various applications. In the present work, alkali ion (Li⁺, Na⁺, K⁺, and Cs⁺) and water configurations in defective PB (d-PB) were studied by using the statistical mechanics of molecular liquids. The three-dimensional (3D) distribution functions of the ions and water were determined by solving the 3D-reference interaction site model (RISM) equation of systems of a unit lattice of d-PB in electrolyte solutions, i.e., LiCl, NaCl, KCl, and CsCl. The results show the difference in the ion–water configurations and distributions between small (Li⁺ and Na⁺) and large ions (K⁺ and Cs⁺). The adsorption sites of Li⁺ and Na⁺ are located off-center and lie on the diagonal axis. By contrast, the larger ions, K⁺ and Cs⁺, are adsorbed at the center of the unit cell. The degree of dehydration due to the adsorption of alkali ions indicates that there was no water exchange during Li⁺ and Na⁺ adsorption, whereas two and three water molecules were removed after adsorption of K⁺ or Cs⁺ in the unit cell.