TY - JOUR
T1 - Distinct ionic adsorption sites in defective Prussian blue
T2 - A 3D-RISM study
AU - Ruankaew, Nirun
AU - Yoshida, Norio
AU - Watanabe, Yoshihiro
AU - Nakayama, Akira
AU - Nakano, Haruyuki
AU - Phongphanphanee, Saree
N1 - Funding Information:
This work was supported by the Kasetsart University Research and Development Institute (KURDI), and Thailand Research fund (No. TRG5780291). NY acknowledges support from Grants-in-Aid (No. 16H00842, 16K05519, 18K05036, and 19H02677) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, and the Toyota RIKEN Scholar Program at the Toyota Physical and Chemical Research Institute. Molecular graphics images were produced using the UCSF Chimera package.65
Publisher Copyright:
This journal is © the Owner Societies.
PY - 2019
Y1 - 2019
N2 - 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.
AB - 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.
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U2 - 10.1039/c9cp04355a
DO - 10.1039/c9cp04355a
M3 - Article
C2 - 31588931
AN - SCOPUS:85073483791
SN - 1463-9076
VL - 21
SP - 22569
EP - 22576
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 40
ER -