• Bulletin of the Korean Chemical Society
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• 제14권2호
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• pp.215-220
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• 1993

Experiment on isomorphous substitution of Al by Fe in sodalite framework was carried out using dry way method at 800-900$^{\circ}$C in nitrogen atmosphere. The substitution of Fe was possible up to 25 mole% with some deviation of symmetry in sodalite cage. The cubic unit cell parameter increased with increasing Fe content. It showed ionic semiconducting property, especially the highest conductivity and the lowest activation energy in 10 mole% Fe-substituted sodalite which could behave as a superionic conductor at above 400$^{\circ}$C. When more Fe was introduced into sodalite the electronic conductivity was improved at high temperature. But the relative electronic contribution was found to be lower compared with ionic contribution at high temperature. In infrared spectra some major absorption bands of sodalite shifted to lower wave numbers due to heavier Fe atoms substitution in Al lattice sites.

• Korean Chemical Engineering Research
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• 제47권4호
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• pp.424-429
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• 2009

물유리로 제조한 알칼리성 실리카-알루미나 합성모액에서 $Na_2O$, $SiO_2$, $H_2O$ 함량이 소달라이트의 결정화도와 입자크기에 미치는 영향을 조사하였다. x=2.5~7.5, y=1.4~3.0, z=140~400 범위에서 한 성분의 함량만 바꾸어 제조한 $x\;Na_2O{\cdot}y\;SiO_2{\cdot}Al_2O_3{\cdot}z\;H_2O$ 조성의 합성모액을 $140^{\circ}C$에서 2일간 수열 반응시켜 소달라이트를 합성하였다. $Na_2O$ 함량이 많아지면 소달라이트의 결정화도가 높아지나 입자는 작아졌다. 합성모액의 $SiO_2/Al_2O_3$ 몰비가 2 근처에서 소달라이트가 생성되었으며, 물의 함량이 달라지면 합성되는 제올라이트의 종류가 달라졌다. 이 합성조건에서는 $SiO_2/Al_2O_3$ 몰비가 2.0 근처이고, $Na_2O$ 함량이 많은 영역에서는 결정화도가 높은 소달라이트가 합성되었으며, 나트륨 이온의 구조유도체로서 효과로 입자 크기는 작아졌다.

• Bulletin of the Korean Chemical Society
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• 제10권3호
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• pp.230-234
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• 1989

The crystal structure of $Ag^+$-exchanged zeolite A vacuum-dehydrated at $370^{\circ}C$ and then treated with carbon monoxide at $$23^{\circ}C$ has been determined by single crystal x-ray diffraction methods in the cubic space group Pm3m at $23^(1){\circ}C$ ; a = 12.116 (2)${\AA}$. The structure was refined to the final error indices $R_1\;=\;0.061\;and\;R_2$(weighted) = 0.068 using 349 independent reflections for which I > 3${\sigma}(I).\;3.6\;Ag_+-CO$ complexes, where -CO may represent -CHO or -$CH_2OH$, were found in each large cavity. By coordination to silver atoms followed by reaction with $Ag^{\circ}and\;H^+$ within the zeolite, carbon monoxide has been partially reduced. In about 28% of the sodalite units, a $Ag_6(Ag^+)_2$ cluster may be present. In about 37% of the sodalite units, three $Ag^+$ ions are found on threefold axes where they may be bridged by three water molecules. The remaining 35% of the sodalite units are empty of silver species. Two $Ag^+$ ions per unit cell are associated with 8-ring oxygens. The remaining ca $$3Ag^+$ ions per unit cell have been reduced during the synthesis and have migrated to form small silver crystallities on the surface of the zeolite single crystal.

• 한국수소및신에너지학회논문집
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• 제14권2호
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• pp.146-154
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• 2003

The hybrids of zeolite and metal hydride were prepared to improve the absorption properties as media for hydrogen storage. The zeolites which was deposited on the surface by metal hydride vapor showed excellent absorption properties and sodalite was proved to be better than zeolite-A in the reaction velocity and hydrogen storage capacity. This suggests the metal hydride could be used effectively as catalytic active material for enhancing the hydrogen storage in zeolite containing $\alpha$-cages and furthermore the hydrogen molecules have preference tobe occluded in their cavities containing $\alpha$-cages more effectively than that containing a and $\beta$-cages.

• Bulletin of the Korean Chemical Society
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• 제15권12호
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• pp.1084-1088
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• 1994

Electrical characteristics of Fe-substituted sodalites were analyzed and equivalent circuits of samples were designed using impedance and admittance data. Internal components of resistances (R$_e$, R$_b$, and R$_{gb}$) and capacitances (C$_b$, C$_dl$ and C$_D$) could be extracted by changing the frequency of measurement at three different temperatures. Upon increasing the temperature, electrical properties of the samples could be elucidated in detail by equivalent circuit. The substitution of Fe on Al site was indirectly confirmed by ESCA and the results explain the lower polarity in Na-O bond of Fe 10 mole ${\%}$-substituted sodalite.

• 한국결정성장학회지
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• 제17권3호
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• pp.95-101
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• 2007

수열합성 장치를 이용하여 종자 결정이 도포된 알루미나 지지체 위에 제올라이트 박막을 합성하였다. X-선 회절 분석과 전자현미경 사진을 이용하여 반응기 내에 생성된 제올라이트 A 분말과 제올라이트 A박막의 생성과 전이 생성물에 대해 합성온도, 합성시간, 종자결정의 영향에 대해서 고찰하였다. 제올라이트 A박막의 생성은 지지체 표면에 도포된 종자 결정에서 치밀한 연속적인 박막이 형성된 다음 용해과정을 거쳐 결정의 크기가 큰 다결정 층을 형성하고, 최종적으로 소다라이트를 거쳐 무정형으로 진행하였다. 반면에 분말에서는 반응초기부터 소다라이트가 관찰되는데 고정된 제올라이트 A 박막과 다르게 결정주위의 공간적인 차이에 의해 소다라이트가 생성하기에 용이한 공간을 갖기 때문에 소다라이트가 쉽게 생성되는 것으로 생각된다. 합성온도가 높으면 짧은 시간 내에 전이 생성물을 거쳐 무정형으로 진행하였고 온도가 낮으면 합성 시간이 길고 피복도가 다소 낮은 제올라이트 A 박막을 얻었다. $120^{\circ}C$, 12시간에서 피복도가 높은 치밀한 제올라이트 A박막을 합성하였다.

• Bulletin of the Korean Chemical Society
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• 제19권11호
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• pp.1222-1227
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• 1998

The crystal structure of a benzene sorption complex of fully dehydrated Cd2+-exchanged zeolite X, Cd46Si100Al92O384·43C6H6 (a=24.880(6) Å), has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21 ℃. The crystal was prepared by ion exchange in a flowing stream of 0.05 M aqueous Cd(NO3)2 for 3 d, followed by dehydration at 400 ℃ and 2 x 10-6 Torr for 2 d, followed by exposure to about 92 Torr of benzene vapor at 22 ℃. The structure was determined in this atmosphere and refined to the final error indices R1=0.054 and Rw=0.066 with 561 reflections for which I > 3σ(I). In this structure, Cd2+ ions are found at four crystallographic sites: eleven Cd2+ ions are at site 1, at the centers of the double six-oxygen rings; six Cd2+ ions lie at site I', in the sodalite cavity opposite to the double six-oxygen rings; and the remaining 29 Cd2+ ions are found at two nonequivalent threefold axes of unit cell, sites Ⅱ' (in the sodalite cavity ) and site Ⅱ (in the supercage) with occupancies of 2 and 27 ions, respectively. Each of these Cd2+ ions coordinates to three framework oxylkens, either at 2.173(13) or 2.224(10) Å, respectively, and extends 0.37 Å into the sodalite unit or 0.60 Å into the supercage from the plane of the three oxygens to which it is bound. The benzene molecules are found at two distinct sites within the supercages. Twenty-seven benzenes lie on threefold axes in the large cavities where they interact facially with the latter 27 site-Ⅱ Cd2+ ions (Cd2+-benzene center=2.72 Å; occupancy=27 molecules/32 sites). The remaining sixteen benzene molecules are found in 12ring planes; occupancy=16 molecules/16 sites. Each hydrogen of these sixteen benzenes is ca. 2.8/3.0 Å from three 12-ring oxygens where each is stabilized by multiple weak electrostatic and van der Waals interactions with framework oxygens.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.190-193
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• 1986

The structure of partially $Ag^+$-exchanged zeolite 4A, $Ag_{7.6}Na_{4.4}-A$, vacuum dehydrated at $370^{\circ}C$, has been determined by single-crystal x-ray diffraction techniques in the cubic space group, Pm3m (a = 12.311(1)${\AA}$) at $24(1)^{\circ}}C$. The structure was refined to the final error indices $R_1$ = $R_2$ (weighted) = 0.064 using 266 independent reflections for which $I_0$>$3{\sigma}(I_0)$. Three $Na^+$ ions occupy the 3 8-ring sites, and the remaining ions, 1.4 $Na^+$ and 6.6 $Ag^+$, fill the 8 6-ring sites; each $Ag^+$ ion is nearly in the [111] plane of its 3 O(3) ligands, and each $Na^+$ ion is 0.9${\AA}$ from its corresponding plane, on the large-cavity side. One reduced silver atom per unit cell was found inside the sodalite unit. It was presumably formed from the reduction of a $Ag^+$ ion by an oxide ion of a residual water molecule or of the zeolite framework. It may be present as a hexasilver cluster in 1/6 of the sodalite units, or, most attractively among several alternatives, as an isolated Ag atom coordinated to 4 Ag ions in each sodalite unit to give $(Ag_5)^{4+}$, symmetry 4mm.

• Bulletin of the Korean Chemical Society
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• 제28권4호
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• pp.567-573
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• 2007

The crystal structure of ZnI2 molecule synthesized in zeolite A (LTA) has been studied by single-crystal X-ray diffraction techniques. A single crystal of |Zn6|[Si12Al12O48]-LTA, synthesized by the dynamic ion-exchange of |Na12|[Si12Al12O48]-LTA with aqueous 0.05 M Zn(NO3)2 and washed with deionized water, was placed in a stream of flowing 0.05 M KI in CH3OH at 294 K for four days. The resulting crystal structure of the product (|K6Zn3(KI)3(ZnI2)0.5|[Si12Al12O48]-LTA, a = 12.1690(10) A) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm3m. It was refined with all measured reflections to the final error index R1 = 0.078 for 431 reflections which Fo > 4σ (Fo). At four crystallographically distinct positions, 3.5 Zn2+ and nine K+ ions per unit cell are found: three Zn2+ and five K+ ions lie on the 3-fold axes opposite 6-rings in the large cavity, two K+ ions are off the plane of the 8-rings, two K+ ions are recessed deeply off the plane of the 8-rings, and the remaining a half Zn2+ ion lie on the 3-fold axes opposite 6-rings in the sodalite cavity. A half Zn2+ ion and an I- ion per unit cell are found in the sodalite units, indicating the formation of a ZnI2 molecule in 50% of the sodalite cavities. Each ZnI2 (Zn-I = 3.35(5) A) is held in place by the coordination of its one Zn2+ ion to the zeolite framework oxygens and by the coordination of its two I- ions to K+ ions through 6-rings (I-K = 3.33(8) A). Three additional I- ions per unit cell are found opposite a 4-ring in the large cavity and form a K3I2+ and two K2ZnI3+ ionic clusters, respectively.

• Bulletin of the Korean Chemical Society
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• 제26권7호
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• pp.1090-1096
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• 2005

$Ag_4Br_4$ nanoclusters have been synthesized in about 75% of the sodalite cavities of fully $K^+$-exchanged zeolite A (LTA). An additional KBr molecule is retained in each large cavity as part of a near square-planar $K_4Br^{3+}$ cation. A single crystal of $Ag_{12}$-A, prepared by the dynamic ion-exchange of $Na_{12}$-A with aqueous 0.05 M $AgNO_3$ and washed with $CH_3OH$, was placed in a stream of flowing 0.05 M KBr in $CH_3OH$ for two days. The crystal structure of the product ($K_9(K_4Br)Si_{12}Al_{12}O_{48}{\cdot}0.75Ag_4Br_4$, a = 12.186(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm m. It was refined with all measured reflections to the final error index $R_1$ = 0.080 for the 99 reflections for which $F_o\;{\gt}\;4_{\sigma}\;(F_o)$. The thirteen $K^+$ ions per unit cell are found at three crystallographically distinct positions: eight $K^+$ ions in the large cavity fill the six-ring site, three $K^+$ ions fill the eight-rings, and two $K^+$ ions are opposite four-rings in the large cavity. One bromide ion per unit cell lies opposite a four-ring in the large cavity, held there by two eight-ring and two six-ring $K^+$ ions ($K_4Br^{3+}$). Three $Ag^+$ and three $Br^-$ions per unit cell are found on 3-fold axes in the sodalite unit, indicating the formation of nano-sized $Ag_4Br_4$ clusters (interpenetrating tetrahedra; symmetry $T_d$; diameter ca. 7.9 $\AA$) in 75% of the sodalite units. Each cluster (Ag-Br = 2.93(3) $\AA$) is held in place by the coordination of its four $Ag^+$ ions to the zeolite framework (each $Ag^+$ cation is 2.52(3) $\AA$ from three six-ring oxygens) and by the coordination of its four $Br^-$ ions to $K^+$ ions through six-rings (Br-K = 3.00(4) $\AA$).