Journal of the Mineralogical Society of Korea (한국광물학회지)

The Mineralogical Society of Korea (한국광물학회)
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Site Competition of Ca2+ and Cs+ Ions in the Framework of Zeolite Y (Si/Al = 1.56) and Their Crystallographic Studies

제올라이트 Y (Si/Al = 1.56) 골격 내의 Ca2+과 Cs+ 이온의 자리 경쟁 및 그들의 결정학적 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 : 2018.10.23
  • Accepted : 2018.11.20
  • Published : 2018.12.31
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Abstract

The present work was performed in order to study the effect of competing cation of $Ca^{2+}$ ion on ion exchange of $Cs^+$ on zeolite Y (Si/Al = 1.56). Three single-crystals of fully dehydrated and partially $Cs^+$-exchanged zeolites Y (Si/Al = 1.56) were prepared by the flow method using mixed ion-exchange solutions. The $CsNO_3:Ca(NO_3)_2$ molar ratios of the ion exchange solution were 1 : 1 (crystal 1), 1 : 100 (crystal 2), and 1 : 250 (crystal 3) with a total concentration of 0.05 M. The single-crystals were then vacuum dehydrated at 723 K and $1{\times}10^{-4}Pa$ for 2 days. The structures of the crystals were determined by single-crystal synchrotron X-ray diffraction technique in the cubic space group $Fd{\bar{3}}m$, at 100(1) K. The unit-cell formulas of crystals 1, 2, and 3 were ${\mid}Cs_{21}Ca_{27}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, ${\mid}Cs_2Ca_{36.5}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, and ${\mid}Cs_1Ca_{37}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, respectively. In all three crystals, the $Ca^{2+}$ ions preferred to occupy site I in the D6Rs, with the remainder occupying sites I', II', and II. On the other hand, the significant differences in the fractional distribution of $Cs^+$ ions are observed depending on the intial $Cs^+$ concentrations in given ion exchange solution. In Crystal 1, $Cs^+$ ion are located at sites II', II, III, and III', and in crystal 2, at sites II, IIIa, and IIIb. In crystal 3, $Cs^+$ ions are only located at sites IIIa and IIIb. The degree of $Cs^+$ ion exchange decreased sharply from 28.0 to 2.7 to 1.3 % as the initial $Ca^{2+}$ concentration increases and the $Cs^+$ content decreases.

본 연구는 제올라이트 Y (Si/Al = 1.56)에서 $Cs^+$ 이온 교환에 $Ca^{2+}$ 이온의 경쟁 양이온 효과를 연구하기 위해 수행되었다. 완전히 탈수되고 부분적으로 $Cs^+$ 이온으로 교환된 3개의 제올라이트 Y(Si/Al = 1.56)의 단결정은 혼합이온교환 용액을 사용하여 흐름법으로 제조되었으며, 전체 농도가 0.05 M인 이온교환용액의 $CsNO_3:Ca(NO_3)_2$ 몰비는 1 : 1 (Crystal 1), 1 : 100 (Crystal 2) 및 1 : 250 (Crystal 3)이다. 이온교환된 단결정을 723 K에서 2일 동안 $1{\times}10^{-4}Pa$로 진공 탈수시켰으며, 결정구조는 100(1) K에서 입방공간군 $Fd{\bar{3}}m$을 사용하여 단결정 싱크트론 X선 회절법으로 해석하고 구조를 정밀화하였다. Crystal 1, 2 및 3의 단위세포당 화학식은 ${\mid}Cs_{21}Ca_{27}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, ${\mid}Cs_2Ca_{36.5}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$ 및 ${\mid}Cs_1Ca_{37}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$이다. 3개의 결정 모두에서, $Ca^{2+}$ 이온은 D6Rs 내의 site I을 우선적으로 점유하고 있으며 나머지는 site I', II' 및 II를 점유하고 있다. 한편 주어진 이온교환용액의 초기 $Cs^+$ 이온의 농도에 따라 $Cs^+$ 이온의 분포에 중요한 차이가 관찰되었다. Crystal 1에서는 $Cs^+$ 이온이 site II', II, III와 III'에 위치하고 있으며, Crystal 2에서는 site II, IIIa, IIIb에 위치하고 있다. Crystal 3에서는 $Cs^+$ 이온은 site IIIa 및 IIIb에만 위치하고 있다. 초기 $Ca^{2+}$ 이온의 농도가 증가하고 $Cs^+$ 이온의 농도가 감소에 따라 $Cs^+$ 이온의 교환정도는 28.0에서 2.7과 1.3 %로 급격히 감소하였다.

Keywords

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