Korean Journal of Mineralogy and Petrology (광물과 암석)

The Petrological Society of Korea & The Mineralogical Society of Korea (한국암석학회 & 한국광물학회)
권호 표지
DOI QR코드

DOI QR Code

Structural Study of Selenium Sorption Complex of Fully Dehydrated, Partially Ca2+-exchanged Zeolite A

완전히 탈수되고 부분적으로 칼슘 이온으로 교환된 제올라이트 A의 셀레늄 수착 화합물의 구조 연구

  • Kim, Hu Sik (Department of Applied Chemistry, Andong National University) ;
  • Park, Jong Sam (Department of Radiologic Technology, Daegu Health College) ;
  • Lim, Woo Taik (Department of Applied Chemistry, Andong National University)
  • Received : 2020.06.09
  • Accepted : 2020.08.20
  • Published : 2020.09.30
Download PDF
⟨ Previous Next ⟩

Abstract

Single crystal of fully dehydrated and partially Ca2+-exchanged zeolites A (|Ca4Na4|[Si12Al12O48]-LTA) was brought into contact with Se in fine pyrex capillary at 523 K for 5 days. Crystal structure of Se-sorbed |Ca4Na4|[Si12Al12O48]-LTA has been determined by single-crystal X-ray diffraction techniques at 294 K in the cubic space group $Pm{\bar{3}}m$ (a = 12.2787(13) Å). The crystal structure of yellow |Ca4Na4Se4|[Si12Al12O48]-LTA has been refined to the final error indices of R1/wR2 = 0.0960/0.3483 with 327 reflections for which Fo > 4s(Fo). In this structure, 4 Na+ and 4 Ca2+ ions fill every 6-ring site: These ions are all found at three crystallographic positions, on 3-fold axes equipoints of opposite 6-rings. Selenium atoms are found at three crystallographically distinct positions: 2 Se atoms per unit cell at Se(1) are located opposite 6-rings in the sodalite cavity (Se(1)-Na(1) = 2.53(5) Å) and 1 at Se(2) opposite 4-rings (Se(2)-O(1) = 2.76(10) Å) and 1 at Se(3) opposite 6-rings in the large cavity (Se(3)-Na(1) = 2.48(5) Å). Two molecular of Se2 (Se(1)-Se(1) = 2.37(7) or 2.90(8) Å and Se(2)-Se(3) = 2.91(5) ) Å) are found in all sodalite cavity and large cavity. Other clusters such as Se4 and Se8 could be existed in large cavity. The inter-selenium distances turned out to be longer that of gases Se2 molecule.

Ca2+ 이온으로 부분적으로 치환된 제올라이트 A (|Ca4Na4|[Si12Al12O48]-LTA) 단결정과 Se을 가는 모세관에 넣은 후 523 K 에서 5일동안 반응을 시켜 Se이 흡착된 제올라이트 A 단결정을 합성 하였다. 이 결정의 구조는 294 K 에서 단결정 X-선 회절 기술을 이용하여 $Pm{\bar{3}}m$ (a = 12.2787(13) Å) 입방 공간군에 속함을 확인 하였고, Fo> 4s(Fo)를 사용하여 최종 오차 인자를 R1/wR2= 0.0960/0.3483로 정밀화 하였다. 이 구조에서는 4개의 Na+와 4개의 Ca2+ 이온이 모든 6-ring 자리에 채워져 있었으며, 이들 이온들은 모두 6-ring 맞은편의 3-fold 축 상의 결정학적 위치에서 발견되었다. Se 원자들은 뚜렷하게 서로 다른 3개의 결정학적 위치에서 발견되었다. 단위 세포당 2개의 Se(1) 원자는 sodalite cavity 내 6-ring 맞은편 (Se(1)-Na(1) = 2.53(5)Å), 1개의 Se(2) 원자는 4-ring 맞은편 (Se(2)-O(1) = 2.76(10) Å), 그리고 1개의 Se(3) 원자는 large cavity 내 6-ring 맞은편 (Se(3)-Na(1) = 2.48(5) Å)에 각각 위치하고 있었다. 2가지 형태의 Se2 분자 (Se(1)-Se(1) = 2.37(7) or 2.90(8) Å and Se(2)-Se(3) = 2.91(5)) Å)가 sodalite cavity와 large cavity 내에서 발견되었으며, Se4와 Se8과 같은 형태의 클러스터가 large cavity 내에 존재할 수 있었다. 이들 클러스터내 Se 원자들 사이의 거리는 기체상태의 Se2 분자내 Se 원자 사이의 거리보다 더 길게 나타났다.

Keywords

References

  1. Armand, P., Saboungi, M.L., Price, D.L., Iton, L., Cramer, C. and Grimsditch, M., 1997. Nanoclusters in zeolite. Physical Review Letters, 79, 2061-2064. https://doi.org/10.1103/PhysRevLett.79.2061
  2. Bogomolov, V.N., Kholodkevich, S.V., Romanov, S.G. and Agroskin. L.S., 1983. The absorption spectra of single selenium and tellurium chains in dielectric matrix channels. Solid State Communications, 47, 181-182. https://doi.org/10.1016/0038-1098(83)90704-4
  3. Bogomolov, V.N., Poborchy, V.V., Romanov, S.G. and Shagin, S.I., 1985. Raman spectra of chalcogen chains isolated in zeolite matrixes. Journal of the Physical Chemistry C: Solid State Physics, 18, L313-L317. https://doi.org/10.1088/0022-3719/18/12/003
  4. Bruker SMART (version 5.0) and SAINT-plus (version 6.0)., 1999, Bruker AXS Inc., Madison, Wisconsin, USA.
  5. Cromer, D.T., 1965. Anomalous dispersion corrections computed from self-consistent field relativistic Dirac-Slater wave functions. Acta Crystallogrphy. 18, 17-23. https://doi.org/10.1107/S0365110X6500004X
  6. Doyle, P.A. and Turner, P.S., 1968, Crystal physics, diffraction, theoretical and general crystallography. Acta Crystallographica A. 24, 390-397. https://doi.org/10.1107/S0567739468000756
  7. Firor, R.L. and Seff. K., 1978. Near zero coordinate $Ca^{2+}\;and\;Sr^{2+}$ in zeolite A. Crystal structures of dehydrated $Ca_{6}-A\;and\;Sr_{6}-A$. Journal of the American Chemical Society, 100, 3091-3096. https://doi.org/10.1021/ja00478a023
  8. Goldbach, A., Iton, L., Grimsditch, M. and Saboungi. M.L., 1996. The formation of $Se_2{^{-}}$: a new resonace Raman feature in the photochemistry of zeolite-encapsulated selenium. Journal of the American Chemical Society, 118, 2004-2007. https://doi.org/10.1021/ja9531788
  9. Heo, N.H., Choi, H.C., Jung, S.W., Park, M. and Seff, K., 1997. Complete redox exchange of indium for $Tl^+$ in zeolite A. Crystal structure of anhydrous $Tl_{12}-A\;and\;In_{10}-A{\cdot}In$. Indium appears as $In^{2+},\;In^{+},\;and\;In^{0}$. The clusters $(In_5)^{8+}\;and\;(In_3)^{2+}$ are proposed. Journal of the Physical Chemistry B, 101, 5531-5539. https://doi.org/10.1021/jp970206v
  10. Herron, N., 1995, Zeolites as Hosts for novel optical and electronic materials. Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, 21, 283-298. https://doi.org/10.1007/BF00709419
  11. Ibers, J. A. and Hamilton, W.C., 1974a, International Tables for X-ray Crystallography, Kynoch Press, Birmingham, England, 71-98.
  12. Ibers, J. A. and Hamilton, W.C., 1974b, International Tables for X-ray Crystallography, Kynoch Press, Birmingham, England, 148-150.
  13. Jang, S.B., Song, S.H. and Kim, Y., 1995, Crystal Structures of bromine sorption complexes of $Ca^{2+}$-exchanged zeolite A. Bulletin of the Korean Chemical Society, 16, 1163-1167.
  14. Kim, S.H., Lim, W.T., Kim, G.H., Lee, H.S. and Heo. N.H., 2006, Synthesis and crystal structure of lead iodide in the sodalite cavities of zeolite A (LTA). Bulletin of the Korean Chemical Society, 27, 679-686. https://doi.org/10.5012/bkcs.2006.27.5.679
  15. Kwon, K.R., 1998. Crystal structure of selenium sorption complex of $Ca^{2+}$-exchanged zeolite A, Korea, ME thesis, Kyungpook National University, 54p.
  16. Parise, J.B., MacDougall, J.E., Herron, N., Farlee, R., Sleight, A.W., Wang, Y., Bein, T., Moller, K. and Moroney, L.M., 1988, Characterization of Se-loaded molecular sieves A, X, Y, AlPO-5, and mordenite. Inorganic Chemistry, 27, 221-228. https://doi.org/10.1021/ic00275a002
  17. Sheldrick, G.M., 1997, SHELXL97, Program for the Refinement of Crystal Structures, University of Gottingen, Germany.
  18. Slater, J.C., 1964, Atomic Radii in crystals. Journal of Chemical Physics, 41, 3199-3205. https://doi.org/10.1063/1.1725697
  19. Tamura, K., Hosokawa, S., Endo, H., Yamasaki, S. and Oyanagi, H., 1986, The isolated Se chains in the channels of mordenite crystal. Journal of the Physical Society of Japan, 55, 528-533. https://doi.org/10.1143/JPSJ.55.528
  20. Weast, R.C., 1989/1990, Handbook of Chemistry and Physics, 70th ed., The chemical Rubber Co.: Cleveland, OH, F-18.