• Bulletin of the Korean Chemical Society
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• 제23권8호
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• pp.1121-1126
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• 2002

Two anhydrous crystal structures of fully dehydrated Cd2+ - and Cs+ -exchanged zeolite X, Cd32Cs28Si100Al92O384 (Cd32Cs28-X: a = 24.828(11) $\AA)$ and fully dehydrated Cd,sup>2+ - and Rb+ -exchanged zeolite X, Cd28Rb36Si100Al92O384 (Cd28Rb36-X: a = 24.794(2) $\AA$), have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ The structures were refined to the final error indices, R1 = 0.058 and R2 = 0.065 with 637 reflections for Cd32Cs28-X and R1 = 0.086 and R2 = 0.113 with 521 reflections for Cd28Rb36-X for which I > $3\sigma(I)$. In the structure of Cd,sub>32Cs28-X, 16 Cd2+ ions fill the octahedral sites I at the centers of the double six rings (Cd-O = $2.358(8)\AA$ and O-Cd-O = $90.8(3)^{\circ}$ ). The remaining 16 Cd2+ ions occupy site II (Cd-O = $2.194(8)\AA$ and O-Cd-O = $119.7(4)^{\circ})$ and six Cs+ ions occupy site II opposite to the single six-rings in the supercage; each is $2.322\AA$ from the plane of three oxygens (Cs-O = 3.193(13) and O-Cs-O = $73.0(2)^{\circ}).$ Aboutten Cs+ ions are found at site II', $1.974\AA$ into the sodalite cavity from their three oxygen plane (Cs-O = $2.947(8)\AA$ and O-Cs-O = $80.2(3)^{\circ}).$ The remaining 12 Cs+ ions are distributed over site III' (Cs-O = 3.143(9) and O-Cs-O= $59.1(2)^{\circ})$. In the structure of Cd28Rb36-X, 16 Cd2+ ions fill the octahedral sites I at the center of the double-sixrings (Cd-O = 2.349(15) and O-Cd-O = $91.3(5)^{\circ}$ ). Another 12 Cd2+ ions occupy two different II sites (Cd-O = $2.171(18)/2.269(17)\AA$ and O-Cd-O = $119.7(7)/113.2(7)^{\circ}).$ Fifteen Rb+ ions occupy site II (Rb-O = $2.707(17)\AA$ and O-Rb-O = $87.8(5)^{\circ}).$ The remaining 21 Rb+ ions are distributed over site III' (Rb-O = $3.001(16)\AA$ and O-Rb-O = $60.7(4)^{\circ})$. It appears that the smaller and more highly charged Cd2+ ions prefer sites I and Ⅱ in that order, and the larger Rb+ and Cs+ ions, which are less able to balance the anionic charge of the zeolite framework, occupy sites II and II' with the remainder going to the least suitable site in the structure, site III'.The maximum Cs+ and Rb+ ion exchanges were 30% and 39%, respectively. Because these cations are too largeto enter the small cavities and their charge distributions may be unfavorable, cation-sieve effects might appear.

• Bulletin of the Korean Chemical Society
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• 제30권8호
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• pp.1703-1710
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• 2009

The single-crystal structure of |$Ca_{35.5}$|[$Si_{121}Al_{71}O_{384}$]-FAU, $Ca_{35.5}Si_{121}Al_{71}O_{384}$ per unit cell, a = 24.9020(10) $\AA$, dehydrated at 673 K and 2 ${\times}\;10^{-6}$Torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd$\overline{3}$m at 294 K. The large single crystals of zeolite Y (Si/Al = 1.70) were synthesized up to diameters of ${\mu}m\;and\;Ca^{2+}$-exchanged zeolite Y were prepared by ion exchange in a batch method of 0.05 M aqueous Ca($NO_3)_2$ for 4 hrs at 294 K. The structure was refined using all intensities to the final error indices (using only the 971 reflections for which $F_o\;>\;4{\sigma}(F_o))\;R_1$ = 0.038 (based on F) and $R_2$ = 0.172 (based on $F^2$). About 35.5 $Ca^{2+}$ ions per unit cell are found at an unusually large number of crystallographically distinct positions, four. Nearly filling site I (at the centers of the double 6-rings), 14.5 octahedrally coordinated $Ca^{2+}$ ions (Ca-O = 2.4194(24) $\AA$ and O-Ca-O = 87.00(8) and 93.00($8^o$) are found per unit cell. One $Ca^{2+}$ ion per unit cell is located at site II’ in the sodalite cavity and extends 0.50 $\AA$ into the sodalite cavity from its 3-oxygen plane (Ca-O = 2.324(13) $\AA$ and O-Ca-O = 115.5(10)o). The remaining twenty $Ca^{2+}$ ions are found at two nonequivalent sites II (in the supercages) with occupancies of 10 and 10 ions, respectively. Each of these $Ca^{2+}$ ions coordinates to three framework oxygens, either at 2.283(3) or 2.333(5) $\AA$, respectively, and extends either 0.24 or 0.54 $\AA$, respectively, into the supercage from the three oxygens to which it is bound. In this crystal, site I is the most populated; sites II’ and II are only sparsely occupied.$Ca^{2+}$+ appears to fit the octahedral site I best. No cations are found at sites III or III’, which are clearly less favorable for $Ca^{2+}$ ions in dehydrated zeolite Y.

• Bulletin of the Korean Chemical Society
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• 제28권2호
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• pp.251-256
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• 2007

The crystal structure of fully dehydrated partially Cs+-exchanged zeolite X, [Cs52Na40Si100Al92O384], a = 24.9765(10) A, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21 °C. The crystal was prepared by flow method for 5 days using exchange solution in which mole ratio of CsOH and CsNO3 was 1 : 1 with total concentration of 0.05 M. The crystal was then dehydrated at 400 °C and 2 × 10-6 Torr for 2 days. The structure was refined to the final error indices, R1 = 0.051 and wR2 (based on F2) = 0.094 with 247 reflections for which Fo > 4σ (Fo). In this structure, about fifty-two Cs+ ions per unit cell are located at six different crystallographic sites with special selectivity; about one Cs+ ion is located at site I, at the centers of double oxygen-rings (D6Rs), two Cs+ ions are located at site I', and six Cs+ ions are found at site II'. This is contrary to common view that Cs+ ions cannot pass sodalite cavities nor D6Rs because six-ring entrances are too small. Ring-opening by the formation of ?OH groups and ring-flexing make Cs+ ions at sites I, I', and II' enter six-oxygen rings. The defects of zeolite frameworks also give enough mobility to Cs+ ions to enter sodalite cavities and D6Rs. Another six Cs+ ions are found at site II, thirty-six are located at site III, and one is located at site III' in the supercage, respectively. Forty Na+ ions per unit cell are located at two different crystallographic sites; about fourteen are located at site I, the centers of D6Rs and twenty-six are also located at site II in the supercage. Cs+ ions and Na+ ions at site II are recessed ca. 0.34(1) A and 1.91(1) A into the supercage, respectively. In this work, the highest exchange level of Cs+ ions per unit cell was achieved in zeolite X by conventional aqueous solution methods and it was also shown that Cs+ ion could pass through the sixoxygen rings.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2785-2788
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• 2012

• Bulletin of the Korean Chemical Society
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• 제33권1호
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• pp.285-288
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• 2012

• 한국물환경학회지
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• 제28권5호
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• pp.723-728
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• 2012

In this study, zeolites were synthesized by a fusion and a hydrothermal methods using a coal fly ash and a waste catalyst. The recovery performance of metal ions on the structure property of synthetic zeolites was evaluated as comparing the adsorption kinetics (Lagergen 2nd order model) and isotherm (Langmuir model) of $Co^{2+},\;Ni^{2+}$, and $Cu^{2+}$ ions. The synthetic zeolites (Z-C1 and Z-W5) were similarly assigned to XRD peaks in a reagent grade Na-A zeolite (Z-WK : $Na_{12}Al_{12}Si_{12}O_{48}\;27.4H_2O$). Adsorption rates of Z-W5 and Z-C1 were in the order of $Cu^{2+}\;>\;Co^{2+}\;>\;Ni^{2+}\;and\;Ni^{2+}\;>\;Cu^{2+}\;>\;Co^{2+}$, respectively. They had influenced upon structure properties of zeolite. Selectivities of metal ions and maximum equilibrium adsorption capacities, $q_{max}$, in Z-C1 and Z-W5 were in the order of $Ni^{2+}$ (127.9 mg/g) > $Cu^{2+}$ (94.7 mg/g) > $Co^{2+}$ (82.6 mg/g) and $Cu^{2+}$ (141.3 mg/g) > $Co^{2+}$ (122.2 mg/g) > $Ni^{2+}$ (87.6 mg/g), respectively. The results show that the synthetic zeolites, Z-C1 and Z-W5, are able to recover metal ions selectively in wastewater.

• Bulletin of the Korean Chemical Society
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• 제13권3호
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• pp.317-324
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• 1992

Structure and dynamics of $Na^+$ ions are investigated by molecular dynamics simulations of rigid dehydrated zeolite-A at several temperatures using a simple Lennard-Jones potential plus Coulomb potential. A best-fitted set of electrostatic charges is chosen from the results of simulation at 298.15 K and Ewald summation technique is used for the long-ranged character of Coulomb interaction. The calculated x, y, and z coordinates of $Na^+$ ions are in good agreement with the positions determined by X-ray crystallography within statistical errors, their random movings in different types of closed cages are well described by time-correlation functions, and $Na_Ⅰ$ type ions are found to be less diffusive than $Na_Ⅱ$ and $Na_{III}$. At 600.0 K, the unstable $Na_{III}$ type ion pushes down one of nearest $Na_{I}$ ions into the $\beta-cage$ and sits on the stable site Ⅰ, and the captured ion in the $\beta-cage$ wanders over and attacks one of 8 $Na_{I}$ type ions.

• 공업화학
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• 제30권6호
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• pp.726-730
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• 2019

본 연구는 제올라이트를 이용한 칼슘이온 제거에 대한 것으로 시멘트 산업에서 발생하는 cement kiln dust를 이용한 CaCO₃ 제조 공정의 문제를 해결하기 위함이다. 칼슘이온을 제거하기 위하여 제올라이트를 개질하여 사용하였으며 결합 양이온 및 구조를 고려한 최적 제올라이트 선정, 칼슘이온 제거 성능 평가, 개질 용액의 종류 및 농도의 영향, K 공존 시 제거 선택도 평가에 대해 연구를 수행하였다. 5종의 제올라이트 중 13X 제올라이트의 칼슘 이온 제거 성능이 가장 우수함을 확인하였고 NaCl 대신 KCl을 개질 용액으로 사용하였을 때 칼슘이온 제거 성능이 증진되는 것을 확인할 수 있었다. 본 연구는 탄산화 공정의 문제 해결, 고농도의 KCl 회수 기술의 바탕이 될 것으로 판단된다.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.348-354
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• 2009

Copper(II) complexes with tetraoxo dithia tetraaza macrocyclic ligands; [18]ane$N_4S_2$: 1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, [20]ane$N_4S_2$: 1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane,Bzo2[18]ane$N_4S_2$: dibenzo-1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, Bzo2[20]ane$N_4S_2$: dibenzo-1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane; were entrapped in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)copper(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); $[Cu(N-N)_2]^{2+}$-NaY; in the nanopores of the zeolite, and (ii) in situ template condensation of the copper(II) precursor complex with thiodiglycolic acid. The obtained complexes and new host-guest nanocomposite materials; $[Cu([18]aneN_4S_2)]^{2+}-NaY,\;[Cu([20]aneN_4S_2)]^{2+}-NaY,\;[Cu(Bzo_2[18]aneN_4S_2)]^{2+}-NaY,\;[Cu(Bzo_2[20]aneN_4S_2)]^{2+}$-NaY; have been characterized by elemental analysis FT-IR, DRS and UV-Vis spectroscopic techniques, molar conductance and magnetic moment data, XRD and, as well as nitrogen adsorption. Analysis of data indicates all of the complexes have been encapsulated within nanopore of zeolite Y without affecting the zeolite framework structure.

• 대한화학회지
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• 제21권3호
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• pp.204-209
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• 1977

경북 구룡포산 천연제올라이트에 대한 물리적 성질과 촉매활성이 검토되었다. 정량분석과 X-선 회절스펙트럼으로부터 천연제올라이트는 30 ${\sim}$ $40{\%}$의 mordenite를 함유하고 있다. 원시료의 표면적은 $75m^2$/g에 불과하나 2N 염산으로 처리시 $320m^2$/g에 이른다. 톨루엔불균화 반응에 대해서도 2N에서 최대의 전화율을 보여주나, 활성저하가 심한 것으로 나타났으며 크실렌에 대한 벤젠의 선택성은 처리한 산농도가 증가함에 따라 감소하는 것으로 나타났다.