Three Crystal Structures of Dehydrated $Ag_{12-x}Na_x-A$ (x = 4, 6, and 8) Treated with Rubidium Vapor

탈수한 $Ag_{12-x}Na_x-A$ (x = 4, 6, 및 8)를 루비듐 증기로 처리한 세가지 결정구조

  • 이현도 (부산대학교 자연과학대학 화학과) ;
  • 김운식 (부산대학교 화학과) ;
  • 박종열 (부산대학교 사범대학 화학교육과) ;
  • 김양 (부산대학교 화학과)
  • Published : 19940300


Three fully dehydrated partially $Ag^+$-exchanged zeolite A(Ag_4Na_8-A, Ag_6Na_6-A, and Ag_8Na_4-A) were treated at $250^{\circ}C$ with 0.1 torr Rb vapor at 4 h. Their structures were determined by singlecrystal X-ray diffraction methods in the cubic space group $Pm{\bar3}m$ (a = 12.264(4) $\AA$, a = 12.269(1) $\AA$, and a= 12.332(3) $\AA$, respectively) at $22(1)^{\circ}C$, and were refined to the final error indices, R(weighed), of 0.056 with 131 reflections, 0.068 with 108 reflections, and 0.070 with 94 reflections, respectively, for which I > $3\sigma(I).$ In these structures, Rb species are found at three different crystallographic sites; three $Rb^+$ ions per unit cell are located at 8-ring centers, ca. 6.0∼6.8 $Rb^+$ ions are found opposite 6-rings on threefold axes in the large cavity, and ca. 2.5 $Rb^+$ ions are found on three fold axes in the sodalite unit. Also, Ag species are found at two different crystallographic sites; ca. 0.6∼1.0 $Ag^+$ ion lies opposite 4-rings and about 1.8∼4.2 Ag atoms are located near the center of the large cavity. In these structures, the numbers of Ag atoms per unit cell are 1.8, 3.0, and 4.2, respectively, and these are likely to form hexasilver clusters at the centers of the large cavities. The $Rb^+$ ions, by blocking 8-rings, may have prevented silver atoms from migrating out of the structure. Each hexasilver cluster is stabilized by coordination to 6-ring, 8-ring $Rb^+$ ions, and also by coordination to a 4-ring $Ag^+$ ion.



  1. J. Am. Chem. Soc. v.99 Kim, Y.;Seff, K.
  2. Ber. Busengens Phys. Chem. v.84 Hermerschmidt, D.;Haul, R.
  3. Surf. Sci. v.156 Grobet, P. J.;Schoonheydt, R. A.
  4. Presented at the 184th National Meeting of the American Chemical Society, INCR71 Ozin, G. A.;Hugues, F.;Mattar, S.;Maintosh, D.
  5. J. Magn. Reson. v.68 Morton, J. R.;Preston, K. P.
  6. In Metal Microstructures in Zeolites Gellens, L. R.;Schoonheydt, R. A.;Jacobs, P. A.(ed.)
  7. J. Phys. Chem. v.96 Song, S. H.;Kim, U. S.;Kim, Y.;Seff, K.
  8. J. Am. Chem. Soc. v.99 Firror, R.;Seff, K.
  9. J. Am. Chem. Soc. v.105 Pluth, J. J.;Smith, J. V.
  10. Handbook of Chemistry and Physics(70th Ed.)
  11. Ph. D. Thesis, University of Hawaii Heo, N. H.
  12. J. Am. Chem. Soc. v.100 Kim, Y.;Seff, K.
  13. J. Phys. Chem. v.88 Seff, K.;Mellum, M. D.
  14. Acc. Chem. Res. v.9 Seff, K.
  15. Caleulations were performed using the Structure Determination Package Programs Frenz, B. A.;Okaya, Y.
  16. International Tables for X-ray Crystallography v.II
  17. Acta Crystallogr., Sect. A. v.24 Doyle, P. A.;Turner, P. S.
  18. Acta Crystallogr. v.18 Cromer, D. T.
  19. J. Phys. Chem. v.89 Blackwell, C. S.;Pluth, J. J.;Smith, J. V.
  20. J. Phys. Chem. v.91 Kim, Y.;Seff, K.
  21. In Metal Microstructures in Zeolites Beyer, H. K.;Jacobs, P. A.;Jacobs, P. A.(ed.)
  22. Bull. Chem. Soc. Jpn. v.45 Tsutsumi, H.;Takahashi, H.
  23. J. Chem. Soc. Faraday Trans. I v.72 Beyer, H. K.;Jacobs, P. A.;Uytterhoeven, J. B.
  24. J. Phys. Chem. v.82 Kim, Y.;Seff, K.
  25. Bull. Korean Chem. Soc. v.5 Kim, Y.;Seff, K.
  26. Bull. Korean Chem. Soc. v.9 Kim, D. S.;Song, S. H.;Kim, Y.