초록
Two crystal structures of fully dehydrated silver and potassium exchanged zeolite A, stoichiometries of $Ag_{9.3}K_{{2.7}^-}A$ (${\alpha}$ = 12.282(2) ${\AA}$) and $Ag_{10.7}K_{{1.3}^-}{\AA}$ (${\alpha}$ = 12.287(2) A) per unit cell, have been determined from 3-dimensional x-ray diffraction data gathered by counter methods. All structures were solved and refined in the cubic space group Pm3m at 21(1)$^{\circ}C$ . The crystals of $Ag_{9.3}K_{{2.7}^-}A$ and $Ag_{10.7}K_{{1.3}^-}A$ were prepared by flow method using exchange solutions in which mole ratios of $AgNO_3$ and $KNO_3$ were 1:10 and 1:5, respectively, with total concentration of 0.05M. The structures of the dehydrated $Ag_{9.3}K_{{2.7}^-}A$ and $Ag_{10.7}K_{{1.3}^-}A$ were refined to yield the final error indices $R_1$ = 0.037 and $R_2$ = 0.040 with 321 reflections, and $R_1$ = 0.042 and $R_2$ = 0.043 with 371 reflections, repectively, for which I > 3${\sigma}$(I). In both structures, eight $Ag^+$ ions are found nearly at 6-ring centers and each $Ag^+$ ion is nearly in the (1 1 1) plane at its O(3) ligands. The 8-ring sites are preferentially occupied by $K^+$ ions in both structures. 1.3 and 1.7 reduced silver atoms per unit cell were found inside of sodalite units of $Ag_{9.3}K_{{2.7}^-}A$ and that of $Ag_{10.7}K_{{1.3}^-}A$, respectively. These reduced silver species were presumably formed from the reduction of $Ag^+$ ions by oxide ions of residual water molecule or of the zeolite framework. These two crystals may be presented as hexasilver cluster in 21.7% and 28.3% of sodalite unit cells for $Ag_{9.3}K_{{2.7}^-}A$ and $Ag_{10.7}K_{{1.3}^-}A$, repectively.