• 분석과학
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• 제18권4호
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• pp.278-286
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• 2005

The crystal structure of ($Tl_{71}$-Y ($Tl_{71}Si_{121}Al_{71}O_{384}$), ${\alpha}=24.706(3){\AA}$, dehydrated at 653 K and $8{\times}10^{-6}$ torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 294(1) K. The structure was refined using all intensities to the final error indices (using only the 302 reflection for which $F_{\circ}$ > $4{\sigma}(F_0)$) $R_1=0.0602$ (based on F) and $R_w=0.1744$ (based on $F_2$). The 71 $Tl^+$ ions per unit cell are found at four crystallographically distinct positions. Site I' position in the sodalite cavity opposite D6Rs are each occupied by eighteen $Tl^+$ ions per unit cell; these $Tl^+$ ions are recessed ca. $1.45{\AA}$ into the sodalite cavity from their O(3) plane (Tl-O=2.701(15), $3.163(16){\AA}$ and O-Tl-O=$92.1(4)^{\circ}$). The 23 $T1^+$ ions fill site II in the supercage; these $T1^+$ ions are recessed ca. $1.58{\AA}$ into the supercage from their O(2) plane (Tl-O = 2.850(16), $3.156(16){\AA}$ and O-T1-O = $85.1(5)^{\circ}$). The 19 $Tl^+$ ions lie at site III' in the supercage near a triple 4-ring (Tl-O = 3.10(7), $3.39(5){\AA}$ and O-Tl-O = 47.8(9), $95.3(18)^{\circ}$) and the remaining II ions occupy another site III' near a triple 4-ring in the supercage (Tl-O = 2.81(4), $2.71(4){\AA}$ and O-Tl-O = $57.3(8)^{\circ}$).

• Bulletin of the Korean Chemical Society
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• 제23권12호
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• pp.1759-1764
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• 2002

Two crystal structures of dehydrated $Ag^+-andTl^+$-exchanged zeolite X$Ag_{27}Tl_{65-}X\;and\;Ag_{23}Tl_{69-}X$have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21(1) $^{\circ}C(a=24.758(4)\AAa=24.947(4)$, ${\AA}respectively).$, Their structures were refined to the final error indices $R_1$=0.055 and $wR_2$=0.057 with 375 reflections, and $R_1$=0.057 and $wR_2$=0.057 with 235 reflections, respectively, for which I > $3\sigma(I).$ In the structure of $Ag_{27}Tl_{65-}X,\;27\;Ag^+$ ions were found at two crystallographic sites: 15$Ag^+$ ions at site I at the center of the hexagonal prism and the remaining 12$Ag^+$ ions at site II' in the sodalite cavity. Sixty-five $Tl^+$ ions were located at three crystallographic sites: 20$Tl^+$ ions at site II opposite single six-rings in the supercage, 18$Tl^+$ ions at site I' in the sodalite cavity opposite the D6Rs, and the remaining 27$Tl^+$ ions at site III' in the supercage. In the structure of $Ag_{23}Tl_{69-}X$, 23$Ag^+$ ions were found at two crystallographic sites: 15 at site I and 8 at site II'. Sixty-nine $Tl^+$ ions are found at four crystallographic sites: 24 at site II, 17 at stie I', and the remaining 28 at two III' sites with occupancies of 22 and 6.

• Bulletin of the Korean Chemical Society
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• 제13권1호
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• pp.70-74
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• 1992

Two crystal structures of ethylene (a= 12.272(2) ${\AA}$) and acetylene (a = 12.245(2) ${\AA}$) sorption complexes of dehydrated fully $Ca^{2+}$-exchanged zeolite A have been determined by single crystal X-ray diffraction techniques in the cubic space group, Pm3m at $21(1)^{\circ}C$. Their complexes were prepared by dehydration at $360^{\circ}C$ and $2{\times}10^{-6}$ Torr for 2 days, followed by exposure to 200 Torr of ethylene gas and 120 Torr of acetylene gas both at $24^{\circ}C$, respectively. The structures were refined to final R (weighted) indices of 0.062 with 209 reflections and 0.098 with 171 reflections, respectively, for which I > 3${\sigma}$(I). The structures indicate that all six $Ca^{2+}$ ions in the unit cell are associated with 6-oxygen ring of the aluminosilicate framework. Four of these extend somewhat into the large cavity where each is coordinated to three framework oxide ions and an ethylene molecule and/or an acetylene molecule. The carbon to carbon distance in ethylene sorption structure is 1.48(7) ${\AA}$ and that in acetylene sorption structure 1.25(8) ${\AA}$. The distances between $Ca^{2+}$ ion and carbon atom are 2.87(5) ${\AA}$ in ethylene sorption structure and 2.95(7) ${\AA}$ in acetylene sorption structure. These bonds are relatively weak and probably formed by the electrostatic attractions between the bivalent $Ca^{2+}$ ions and the polarizable ${\pi}$-electron density of the ethylene and/or acetylene molecule.

• Bulletin of the Korean Chemical Society
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• 제10권3호
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• pp.234-238
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• 1989

The crystal structure of partially $Ag^+$-exchanged zeolite A, $Ag_{3.2}Na_{8.8}$-A, vacuum dehydrated at $360^{\circ}C$ and then exposed to 0.1 torr of cesium vapor for 12 hours at $250^{\circ}C$ has been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m (a = 12.262(2)${\AA})\;at\;21(1)^{\circ}C$. The structure was refined to the final error indexes $R_1=0.068\;and\;R_2=0.072$ by using 338 reflections for which $I_o\;>\;3{\sigma}(I_o)$ and the composition of unit cell is $Ag_{3.2}Cs_{8.8}-A.\;3\;Cs^+$ ions lie on the centers of the 8-rings at sites of D4h symmetry. Two crystallographycally different 6-ring $Cs^+$ ions were found: 1.5 $Cs^+$ ions at Cs(2) are located inside of sodalite cavity and 4.3 $Cs^+$ ions at Cs(3) are located in the large cavity. The fractional occupancies observed at Cs(2) and Cs(3) indicate that the existence of at least three types of unit cells with regard to the 6-ring $Cs^+$ ions. For example, 50% of unit cells may have two $Cs^+$ ions at Cs(2) and 4 $Cs^+$ ions at Cs(3). 30% of unit cells may have one Cs+ ion at Cs(2) and 5 $Cs^+$ ions at Cs(3). The remaining 20% would have one $Cs^+$ ion at Cs(2) and 4 $Cs^+$ ions at Cs(3). On threefold axes of the unit cell two non-equivalent Ag atom positions are found in the large cavity, each containing 0.64 and 1.92 Ag atoms, respectively. A crystallographic analysis may be interpreted to indicate that 0.64 $(Ag_5)^+$ clusters are present in each large cavity. This cluster may be viewed as a tetrasilver molecule $(Ag_4)^0$(bond length, 2.84${\AA}$) stabilized by the coordination of one $Ag^+$ ion.

• 대한화학회지
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• 제35권3호
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• pp.189-195
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• 1991

탈수한 $(Ag_{2.8}Zn_{4.6}-A)$의 구조와 이 결정에 에틸렌 기체가 흡착된 구조를 X-선 단결정 회절법으로 입방공간군인 Pm3m을 사용하여 구조를 해석하고 정밀화시켰다. $Ag^+$ 이온 및 $Zn^{2+}$ 이온으로 이온교환시킨 두 개의 결정을 400$^{\circ}$C, $2.0{\times}10^{-6}$Torr의 진공하에서 2일간 탈수시킨 후, 그 중 하나의 결정에는 25(1)$^{\circ}$C에서 250 Torr의 에틸렌 기체를 1시간 동안 처리하였다. 탈수한 $Ag_{2.8}ZN_{4.6}-A$ (a = 12.137(2) ${\AA}$)의 결정구조는 I > 3${\sigma}$(I)인 237개의 회절점을 사용하여 $R_w$ 값이 0.044까지 정밀화시켰고, 에틸렌을 흡착시킨 $Ag_{2.8}ZN_{4.6}-A{\cdot}5.6C_2H_4$(a = 12.137(2) ${\AA}$)의 결정구조에서는 301개의 회절점을 사용하여 $R_w$값이 0.050까지 정밀화시켰다. 2.8개의 $Ag^+$ 이온은 에틸렌 분자와 ${\pi}$착물을 형성하며, 6-링 평면에서 큰 동공쪽으로 0.922(2) ${\AA}$이동한 위치에 골조의 산소와 2.240(5)${\AA}$에서 결합하고 있었고, 에틸렌 분자의 탄소원자와 2.290(5)${\AA}$에서 결합하고 있었다. $Zn^{2+}$ 이온은 단위세포단 두 개의 서로 다른 3회 회전축상에 위치하고 있으며, 이 중 2.8개의 $Zn^{2+}$ 이온은 에틸렌 분자와 ${\pi}$착물을 형성하며, (111) 평면에서 큰 동공쪽으로 0.408(2)${\AA}$이동한 위치에 골조의 산소와 결합하고 있었다. $Zn^{2+}$ 이온과 에틸렌 분자의 탄소원자간 결합거리는 2.78(4)${\AA}$이며, 이는 비교적 약한 결합임을 나타낸다.

• 대한화학회지
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• 제40권7호
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• pp.474-482
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• 1996

$Ag^+$ 이온으로 완전히 치환되고 탈수된 두개의 제올라이트 X의 구조(a=24.922${\AA}$, a=24.901(1)${\AA}$)를 21$^{\circ}C$에서 입방공간군 Fd3을 사용하여 단결정 X-선 회절법으로 해석하고 구조를 정밀화하였다. 결정은 $AgNO_3$의 수용액을 사용하여 3일간 흐름법으로 이온 교환하였다. 첫번째 결정은 300$^{\circ}C$에서 $2{\times}10^{-6$torr하에서 2일간 진공 탈수하였다. 두번째 결정은 350$^{\circ}C$에서 진공 탈수하였다. 첫번째 구조는 Full-matrix 최소자승법 정밀화 계산에서 I>3${\sigma}$(I)인 227개의 독립 반사를 사용하여 최종 오차 인자를 $R_1=0.095,\;R_2=0.092$까지 정밀화 계산하였고, 두번째 구조는 334개의 독립 반사를 사용하여 $R_1=0.096,\;R_2=0.087$까지 정밀화시켰다. 첫번째 결정에서 Ag는 서로 다른 5개의 결정학적 자리에 위치하였다. 16개의 $Ag^-$이온은 D6R의 중심에 있는 자리 I를 채우면서 위치하고, 32개의 Ag원자는 D6R의 맞은편에 있는 소다라이트 공동에 있는 자리 I'에 위치하였고, 17개의 $Ag^+$ 이온은 큰 공동에 있는 6-산소 링에서 소다라이트 공동 내의 32-중축을 가진 II'에 위치하고, 15개의 $Ag^+$ 이온은 큰 공동에 32-중축을 가진 II에 위치하고, 나마지 12개의 $Ag^+$이온은 2중축을 약간 벗어난 큰 공동에 있는 III'에 위치하였다. 두번째 결정에서 모든 Ag종은 첫번째 결정과 유사한 자리에 있었다. 자리 I에 16개, 자리 I'에 28개, 자리 II에 16개, 자리 II'에 16개, 자리 III에 6개 또 다른 III'에 6개 모두 88개의 Ag종이 위치하였고 4개의 Ag원자는 탈수중에 골조 밖으로 이동하였다. 이들 결정에서 Ag원자는 소다라이트 공동의 중심에서 사면체의 $Ag_4$ 클라스터를 형성하였다. 이 클라스터는 2개의 $Ag^+$이온과 배위하여 안정화 된다. 클라스터에서 Ag-Ag 거리는 약 3.05.angs.이고 은금속에서 Ag-Ag 거리인 2.89.angs.보다 약간 길었다. 소다라이트 공동에 위치한 자리II에서 적어도 2개의 6-링에 위치한 $Ag^+$이온은 클라스터에 반드시 배위하며, 뒤틀린 팔면체 은 클라스터인($Ag_6)^{2+}$)로 존재한다.

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.603-610
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• 1993

The crystal structure of dehydrated $Ag_{5.6}K_{6.4}-A$, zeolite A ion-exchanged with $K^+\;and\;Ag^+$ as indicated and dehydrated at 360$^{\circ}$C, has been determined by single-crystal X-ray diffraction techniques. Also determined were the structures of the products of the reactions of this zeolite with 0.1 Torr of Cs vapor at 250$^{\circ}$C for 48 h and 72 h, and with 0.1 Torr of Rb vapor at 250$^{\circ}$C for 24 h. The structures were solved and refined in the cubic space group Pm3m at 21(l)$^{\circ}$C (a= 12.255(l) ${\AA}$ , 12.367(l) ${\AA}$, 12.350(l) ${\AA}$, and 12.263(l) ${\AA}$, respectively). Dehydrated $Ag_{5.6}K_{6.4}$-A was refined to the final error indices $R_1= 0.044\;and\;R_2=0.037$ with 202 reflections for which I>3${\sigma}$(I). The crystal structures of the reaction products were refined to $R_1=0.087\;and\;R_2= 0.089$ with 157 reflections, $R_1=0.080\;and\;R_2= 0.087$ with 161 reflections, and $R_1= 0.071\;and\;R_2=0.061$ with 88 reflections, respectively. In the structure of $Ag_{5.6}K_{6.4}-A,\;K^+$ ions block all 8-oxygen rings, and one reduced Ag atom is found per sodalite cavity. Also, ca. 4.6 $Ag^+ ions\;and\;3.4 K^+ ions$ are found at 6-ring sites in the large cavity. The crystal structures of the reaction products show that all $K^+$ and $Ag^+$ ions have been reduced, and that all K^+$ atoms have left the zeolite. Cs or Rb species are found at three different crystallographic sites: 3.0 $Cs^+\;or\;3.0Rb^+$ ions per unit cell occupy 8-ring centers, ca. 8.0 $Cs^+ ions\;or\;5.7 Rb^+$ ions, are found on threefold axes opposite 6-rings deep in the large cavity, and ca. 2.5 $Cs^+\;or\;2.3 Rb^+ ions are found on threefold axes in the sodalite unit. Also, 1 $Rb^+$ ion lies opposite a 4-ring. Silver atoms, corresponding to 75% or 40% occupancy of hexasilver clusters stabilized by coordination to $Cs^+\;or\;Rb^+$ ions, are found at the centers of the large cavities. In the crystal structures of dehydrated Ag_{5.6}K_{6.4}-A$ reacted with Cs vapor, excess Cs atoms are absorbed and these form (locally) cationic clusters such as $(Cs_4)3^+\;and\;(Cs_6)4^+$.

• 대한화학회지
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• 제33권1호
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• pp.18-24
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• 1989

X-선 단결정법으로 탈수한 $Ag_{9}Rb_{3}-A$ (a = 12.278(2)${\AA}$) 와 $Ag_{10}Rb_{2}-A$ (a = 12.286(2)${\AA}$)의 구조를 입방공간군 Pm3m을 써서 해석하였다. $Ag_{9}Rb_{3}-A$의 구조는 I >3${\sigma}$(I)인 회절반점 291개를 이용하여 $R_1$ = 0.064, $R_2$ = 0.060까지 정밀화 시켰으며 $Ag_{10}Rb_{2}-A$의 구조는 416개의 회절반점을 이용하여 $R_1$ = 0.063, $R_2$ = 0.080까지 정밀화 시켰다. 두 구조 모두 단위세포당 하나의 환원된 은 원자가 소다라이트 동공 내에 있으며 이 환원된 은 원자는 소다라이트 동공 1/6개 마다 $Ag_6$로 존재하든가 혹은 모든 소다라이트 동공마다 4mm 대칭성을 가지는 $(Ag_5)^{4+}$ 클러스터로 존재한다. 그 밖에 탈수한 $Ag_{9}Rb_{3}-A$에서는 8개의 $Ag^+$이온은 6-링 중심 3회 회전축 상에 있으며 3개의 $Rb^+$이온은 8-링 중심 $D_{4h}$ 대칭성을 가지고서 위치하고 있다. 또 탈수한 $Ag_{10}Rb_{2}-A$구조에서는 2개의 다른 6-링 $Ag^+$ 이온 즉 7개의 $Ag^+$ 이온은 6-링 평면상에 위치하고 1개의 $Ag^+$이온은 소다라이트 동공 내에 위치한다. 두 개의 서로 다른 8-링 양이온이 있으며 두 개의 $Rb^+$이온은 8-링 중심에 위치하였고 1개의 $Ag^+$이온은 8-링에서 0.1$\AA$ 만큼 큰 동공 쪽으로 이동하여 위치한다. 두 구조에서 보면 $Ag^+$이온은 6-링 위치에 $Rb^+$ 이온은 8-링 위치에 우선적으로 위치한다.

• 대한화학회지
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• 제57권1호
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• pp.12-19
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• 2013

The single-crystal structure of fully dehydrated partially $Li^+$-exchanged zeolite Y, ${\mid}Li_{50}Na_{25}{\mid}[Si_{117}Al_{75}O_{384}]$-FAU, was determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 100(1) K. Ion exchange was accomplished by flowing stream of 0.1 M aqueous $LiNO_3$ for 2 days at 293 K, followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. The structure was refined using all intensities to the final error indices (using only the 801 reflections with ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2=0.043/0.140$. The 50 $Li^+$ ions per unit cell are found at three different crystallographic sites. The 19 $Li^+$ ions occupy at site I' in the sodalite cavity: the $Li^+$ ions are recessed 0.30 ${\AA}$ into the sodalite cavity from their 3-oxygens plane (Li-O = 1.926(5) ${\AA}$ and $O-Li-O=117.7(3)^{\circ}$). The 20 $Li^+$ ions are found at site II in the supercage, being recessed 0.23 ${\AA}$ into the supercage (Li-O = 2.038(5) ${\AA}$ and $O-Li-O=118.7(3)^{\circ}$). Site III' positions are occupied by 11 $Li^+$ ions: these $Li^+$ ions bind strongly to one oxygen atom (Li-O = 2.00(8) ${\AA}$). About 25 $Na^+$ ions per unit cell are found at four different crystallographic sites: 4 $Na^+$ ions are at site I, 5 at site I', 12 at site II, and the remaining 4 at site III'.

• Bulletin of the Korean Chemical Society
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• 제8권2호
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• pp.69-72
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• 1987

The structures of dehydrated $Ag_9Cs_3$-A treated with hydrogen gas at three different temperatures have been determined by single-crystal X-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at 23(1) $^{\circ}C$. All crystals were ion exchanged in flowing streams of aqueous $AgNO_3$/$CsNO_3$ with a mole ratio 1:3.0 to achieve the desired crystal composition. The structures treated with hydrogen at $23^{\circ}C(a=12.288(1)\;{\AA})\;and\;310^{\circ}C(a=12.291(2)\;{\AA})$ refined to the final error indices R1 = 0.091 and R2 = 0.079, and 0.065 and 0.073, respectively, using the 216 and 227 reflections, respectively, for which I >3${\sigma}$(I). In both of these structures, eight $Ag^+$ ions are found nearly at 6-ring centers, and three $Cs^+$ ions lie at the centers of the 8-rings at sites of $D_{4h}$ symmetry. One $Ag^{\circ}atom$, presumably formed from the reduction of a $Ag^+$ ion by an oxide ion of a residual water molecule or of the zeolite framework during the dehydration process, is retained within the zeolite, perhaps in a cluster. In these two structures hydrogen gas could not enter the zeolite to reduce the $Ag^+$ ions because the large $Cs^+$ ions blocked all the 8-windows. However, hydrogen could slowly diffuse into the zeolite and was able to reach and to reduce about half of the $Ag^+$ ions in the structure only at high temperature ($470^{\circ}C$). The silver atoms produced migrated out of the zeolite framework, and the protons generated led to substantial crystal damage.