• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.18-24
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• 1989

Two crystal structures of dehydrated $Ag^+$ and $Rb^+$ exchanged zeolite A, stoichiometries of $Ag_{9}Rb_{3}-A$ (a = 12.278(2)${\AA}$) and $Ag_{10}Rb_{2}-A$ (a = 12.286(2)${\AA}$) per unit cell, have been determined by single crystal x-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at 21(1)$^{\circ}$C. The crystals of $Ag_{10}Rb_{2}-A$ and $Ag_{10}Rb_{2}-A$ were prepared by flow methods using exchanged solution in which mole ratios of AgNO$_3$ and RbNO$_3$ were 1:5 and 1:50, respectively, with the total concentration of 0.05 M. The structures of the dehydrated $Ag_{9}Rb_{3}-A$ and the $Ag_{10}Rb_{2}-A$ were refined to the final error indices, $R_1$ = 0.064 and $R_2$ = 0.060 with 291 reflections, and $R_1$ = 0.063 and $R_2$ = 0.080 with 416 reflections respectively, for which I >3${\sigma}$(I). In both structures, one reduced silver atom per unit cell was found inside the sodalite cavity. It may be present as a hexasilver cluster in 1/6 of the sodalite units or as an isolated Ag atom coordinated to 4 $Ag^+$ ions in each sodalite unit to give $(Ag_5)^{4+}$, symmetry 4 mm. In the structure of dehydrated $Ag_{9}Rb_{3}-A$, 8 $Ag^+$ ions lie on the threefold axis and each is nearly at the center of the 8-rings at the sites of $D_{4h}$ symmetry. In the structure of dehydrated $Ag_{10}Rb_{2}-A$, two crystallographically different eight 6-ring $Ag^+$ ions were found; $7Ag^+$ ions in the (111) planes of their O(3) framework oxygens and one $Ag^+$ ion inside of sodalite cavity. Two crystallographically different 8-ring cations were also found; two $Rb^+$ ions at the centers of the 8-oxygen rings and one $Ag^+$ ion into the large cavity. Both structures indicate that $Rb^+$ ions prefer to occupy the 8-ring sites, while $Ag^+$ ions prefer to occupy the 6-ring sites.

• Journal of the Mineralogical Society of Korea
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• v.4 no.1
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• pp.22-31
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• 1991

Three crystal structures of dehydrated $Ag^+$-and $Ca^{2+}$- exchanged zeolite $A(Ag_4Ca_4-A,\;Ag_^Ca_3-A,\;and\;Ag_8Ca_2-A)$ treated at 250${\circ}C$ with 0.1 Torr of Rb vapor have been determined by single-crystal x-ray diffraction techniques in the cubic space group Pm3m at 21(1)${\circ}C$ (a=12,271(1)${\AA}$, 12.255(1)${\AA}$, and 12.339(1)${\AA}$, respectively). Their structures were refined to the final error indices. R(weighted) of 0.072 with 130 reflections, 0.050 with 110 reflections, and 0.083 with 86 reflections, respectively, for which $I>3{\rho}(I)$. In each structure, Rb species are found at three different crystallographic sites:3$Rb^+$+ions per unit cell are located at 8-ring centers, ca. 5.6 to 6.4 $Rb^+$ ions are found opposite 6-rings on threefold axes in the large cavity, and ca. 2.5 to 3.0 $Rb^+$ ions are found on threefold axes in the sodalite unit. Also, Ag species are found at two different crystallographic stites: ca. 0.7 to 2.1 $Ag^+$ lie opposite 4-rings and ca. 2.2 to 4.8 Ag atoms are located near the center of the large cavity. In these structures, the numbers of Ag atoms per unit cell are 2.2, 2.4, and 4.8, respectively, and these may form hexasilver clusters at the centers of the large cavities. The $Rb^+$ ions, by blocking 8-rings, may have prevented silver from migrating out of the structure. Each hexasilver cluster is stabilized by coordination to up to 13 $Rb^+$ions. An excess absorption of about 0.8 Rb atom per unit cell indicates that the presence of a triangular symmetric $(Rb_3)2^{+}$ cation in sodalite cavity. At least one large-cavity six-ring $Rb^+$ ion must necessarily approach this cluster and may be viewed as a member of it to give $(Rb)_4^{3+}$, $(Rb)_5^{4+}$ or $(Rb)_6^{5+}$.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.4
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• pp.447-455
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• 2022

Fully dehydrated Tl₁₂-LTA (|Tl₁₂|[Si₁₂Al₁₂O₄₈]-LTA,Tl₁₂-A) was treated with 6.0×10³ Pa of ZrI₄ (g) at 623 K for 72 hr under anhydrous conditions. The crystal structure of product, |Zr_0.25I_1.5Tl₁₂|[Si₁₂Al₁₂O₄₈]-LTA, was determined by single-crystal crystallography using synchrotron X-radiation in the cubic space group Pm3m (a = 12.337(2) Å). It was refined using all data to the final error index (for the 712 unique reflections for which F_o> 4σ(F_o) R₁/wR₂= 0.055/0.189. In this structure, octahedral ZrI₆^2- ions center about 25% of the large cavities (Zr-I = 2.91(4) Å). Each coordinates to eight Tl⁺ ions and they are further bridged by Tl⁺ ions in the planes of 8-rings to form a cubic three-dimensional ZrI₆Tl₁₁⁹⁺ cationic cluster. About 1.5 Tl⁺ ions per unit cell moved to deeper side of sodalite cavity after reaction with ZrI₄(g). The remaining Tl⁺ ions occupy well-established cation positions near 6- and 8-rings.

• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.520-527
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• 1988

The crystal structures of $Co^{2+}\;and\;Ag^+\;exchanged\;zeolite\; A,\; Ag_6Co_3$-A(a = 12.131(5)$\AA$) and $Ag_3Co_{4.5}$-A(a = 12.145(1)$\AA$), have been determined by single crystal X-ray diffraction techniques. Both structures were solved and refined in the cubic space group Pm3m at 21(1)$^{\circ}C$. Full-matrix leastsquares refinement converged to the final error indices of R1 = 0.045 and R2 = 0.041 for $Ag_3Co_{4.5}-A,\; and\; R1 = 0.066\; and\; R2 = 0.076\; for\; Ag_6Co_3$-A using the 258 and 189 reflections, respectively, for which I > 3$\sigma$(I). Both structures indicate that CO(Ⅱ)ions are coordinated by three framework oxygens; the Co(II) to O(3) distances are 2.118(4)$\AA$ for $Ag_3Co_{4.5}$-A and 2.106(1)$\AA$ for $Ag_6Co_3-A$, respectively. In each structure, the angle substended at Co(II), O(3)-Co(II)-O(3) is ca 120°, close to the idealized trigonalplanar value. $Co^{2+}$ ions prefer to 6-ring sites and $Ag^+$ ions prefer to 8-ring site when total number of cations is more than 8. The crystals of hydrated and dehydrated $Ag_{12-2x}Co_x-A (x > 4.5)$ had no crystalline diffraction pattern, indicating the apparent exchange limit of $Co^{2+}\; into\; Ag_{12}-A\; is\; 4.5 Co^{2+}$ ions per unit cell. $Co^{2+}$ ions hydrolyze $H_2O$ molecules and $H_3O^+$ concentraction is accumulating. These $H_3O^+$ ions destroy the zeolite structures.

• Journal of the Korean Chemical Society
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• v.38 no.3
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• pp.186-196
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• 1994

Three fully dehydrated partially $Ag^+$-exchanged zeolite A(Ag_4Na_8-A, Ag_6Na_6-A, and Ag_8Na_4-A) were treated at $250^{\circ}C$ with 0.1 torr Rb vapor at 4 h. Their structures were determined by singlecrystal X-ray diffraction methods in the cubic space group $Pm{\bar3}m$ (a = 12.264(4) $\AA$, a = 12.269(1) $\AA$, and a= 12.332(3) $\AA$, respectively) at $22(1)^{\circ}C$, and were refined to the final error indices, R(weighed), of 0.056 with 131 reflections, 0.068 with 108 reflections, and 0.070 with 94 reflections, respectively, for which I > $3\sigma(I).$ In these structures, Rb species are found at three different crystallographic sites; three $Rb^+$ ions per unit cell are located at 8-ring centers, ca. 6.0∼6.8 $Rb^+$ ions are found opposite 6-rings on threefold axes in the large cavity, and ca. 2.5 $Rb^+$ ions are found on three fold axes in the sodalite unit. Also, Ag species are found at two different crystallographic sites; ca. 0.6∼1.0 $Ag^+$ ion lies opposite 4-rings and about 1.8∼4.2 Ag atoms are located near the center of the large cavity. In these structures, the numbers of Ag atoms per unit cell are 1.8, 3.0, and 4.2, respectively, and these are likely to form hexasilver clusters at the centers of the large cavities. The $Rb^+$ ions, by blocking 8-rings, may have prevented silver atoms from migrating out of the structure. Each hexasilver cluster is stabilized by coordination to 6-ring, 8-ring $Rb^+$ ions, and also by coordination to a 4-ring $Ag^+$ ion.

• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.7-13
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• 1995

The crystal sructures of $X(Ca_{46}Al_{92}Si_{100}O_{384})$ and $Ca_{32}K_{28}-X(Ca_{32}K_{28}Al_{92}Si_{100}O_{384})$ dehydrated at $360^{\circ}C$ and $2{\times}10^{-6}$ Torr have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ Their structures were refined to the final error indices, R_1=0.096,\;and\;R_2=0.068$ with 166 reflections, and R_1=0.078\;and\;R_2=0.056$ with 130 reflections, respectively, for which I > $3\sigma(I).$ In dehydrated $Ca_{48}-X,\;Ca^{2+}$ ions are located at two different sites opf high occupancies. Sixteen $Ca^{2+}$ ions are located at site I, the centers of the double six rings $(Ca(1)-O(3)=2.51(2)\AA$ and thirty $Ca^{2+}$ ions are located at site II, the six-membered ring faces of sodalite units in the supercage. Latter $Ca^{2+}$ ions are recessed $0.44\AA$ into the supercage from the three O(2) oxygen plane (Ca(2)-O(2)= $2.24(2)\AA$ and $O(2)-Ca(2)-O(2)=119(l)^{\circ}).$ In the structure of $Ca_{32}K_{28}-X$, all $Ca^{2+}$ ions and $K^+$ ions are located at the four different crystallographic sites: 16 $Ca^{2+}$ ions are located in the centers of the double six rings, another sixteen $Ca^{2+}$ ions and sixteen $K^+$ ions are located at the site II in the supercage. These $Ca^{2+}$ ions adn $K^+$ ions are recessed $0.56\AA$ and $1.54\AA$, respectively, into the supercage from their three O(2) oxygen planes $(Ca(2)-O(2)=2.29(2)\AA$, $O(2)-Ca(2)-O(2)=119(1)^{\circ}$, $K(1)-O(2)=2.59(2)\AA$, and $O(2)-K(1)-O(2)=99.2(8)^{\circ}).$ Twelve $K^+$ ions lie at the site III, twofold axis of edge of the four-membered ring ladders inside the supercage $(K(2)-O(4)=3.11(6)\AA$ and $O(1)-K(2)-O(1)=128(2)^{\circ}).$

• Clean Technology
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• v.24 no.1
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• pp.41-49
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• 2018

Y zeolites with different extra-framework cations, such as $Na^+$, $N^+$, $Ca^{2+}$, and $Cu^{2+}$, with different charge and ionic radius have been investigated to greatly enhance a working capacity (W) of $CO_2$ adsorption at $25^{\circ}C$ and a $CO_2/CO$ selectivity factor (S). A sample of NaY with a very small amount of 0.012% $Ca^{2+}$ was fully reversible for seven times repeated $CO_2$ adsorption/desorption cycles, thereby forming no surface carbonates unlikely earlier reports. Although at pressures above 4 bar, 2.00% CaY, 1.60% CuY and 1.87% LiY all showed a $CO_2$ adsorption very similar to that measured for NaY, they gave a significant decrease in the adsorption at lower pressures, depending on the metal ion. At 0.5 ~ 2.5 bar, the extent of $CO_2$ adsorption was in the order NaY > 1.60% CuY > 2.00% CaY > 1.87% LiY. All the $Na^+-based$ metals-exchanged zeolites have a FAU (faujasite) framework and a Si/Al value near 2.6; thus, there is no discernible difference in the framework topology, framework chemical compositions, effective aperture size, and channel structure between the zeolite samples. Therefore, the distinctive behavior in the adsorption of $CO_2$ with a character as a weak Lewis acid is associated with the site basicity of the zeolites, and the interaction potentials of the cations. Different trend was shown for a CO adsorption due to weaker quadrupole interactions. Adsorption of $CO_2$ and CO on samples of CaY with 0.012 to 5.23% Ca disclosed a significant dependence on the Ca loading. The $CO_2$ adsorption increased when the cation exists up to ca. 0.05%, while it decreased at higher Ca amounts. However, values for both W and S could greatly increase as the bare zeolite is enriched by $Ca^{2+}$ ions. The 5.23% CaY had $W=2.37mmol\;g^{-1}$ and S = 4.37, and the former value was comparable to a benchmark reported in the literature.

• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.384-385
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• 1999

Two anhydrous crystal structures of fully dehydrated, $Ca^{2+}$- and $Tl^+$-exchanged zeolite X, TEX>$Ca_{18}Tl_{56}Si_{100}Al_{92}O_{384}($Ca_{18}Tl_{56}$-X;\alpha=24.883(4)\AA)$ and TEX>$Ca_{32}Tl_{28}Si_{100}Al_{92}O_{384}($Ca_{32}Tl_{28}$-X;\alpha=24.973(4)\AA)$ per unit cell, have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ $Ca_{18}Tl_{56}-X$ was prepared by ion exchange in a flowing stream of 0.045 M aqueous $Ca(NO_3)_2$ and 0.005 M $TlNO_3$. $Ca_{32}Tl_{28}-X$ was prepared similarly using a mixed solution of 0.0495 M $Ca(NO_3)_2$ and 0.0005M $TlNO_3$. Each crystal was then dehydrated at 360 $^{\circ}C$ and $2{\times}10^{-6}$ Torr for 2 days. Their structures were refined to the final error indices, $R_1=0.039\;and\;R_2=0.036$ with 382 reflections for $Ca_{18}Tl_{56}-X$ , and $R_1=0.046\;and\;R_2=0.045$ with 472 reflections for $Ca_{32}Tl_{28}$-X for which $/>3\sigma(I).$ In the structures of dehydrated $Ca_{18}Tl_{56^-}X\;and\;Ca_{32}Tl_{28}$-X, $Ca^{2+}\;and\;Tl^+$ ions are located at six crystallographic sites. Sixteen $Ca^{2+}$ ions fill the octahedral sites I at the centers of double six rings ($Ca_{18}Tl_{56}$-X:Ca-O=2.42(1) and O-Ca-O=93.06(4)$^{\circ}$; $Ca_{32}Tl_{28}$-X Ca-O=2.40(1) $\AA$ and O-Ca-O=93.08(3)$^{\circ}$). In the structure of $Ca_{18}Tl_{56}$-X, another two $Ca^{2+}$ ions occupy site II (Ca-O=2.35(2) $\AA$ and O-Ca-O=111.69(2)$^{\circ}$) and twenty six $Tl^+$ ions occupy site II opposite single six-rings in the supercage; each is 1.493 $\AA$ from the plane of three oxygens $(Tl-O=2.70(8)\AA$ and O-Tl-O=92.33(4)$^{\circ}$). About four $Tl^+$ ions are found at site II',1.695 $\AA$ into sodalite cavity from their three oxygen plane (Tl-O=2.81 (1) and O-Tl-O=87.48(3)). The remaining twenty six $Tl^+$ ions are distributed over site III'(Tl-O=2.82 (1) $\AA$ and Tl-O=2.88(3)$^{\circ}$). In the structure of $Ca_{32}Tl_{28}$-X, sixteen $Ca^{2+}$ ions and fifteen $Tl^+$ ions occupy site III' (Ca-O=2.26(1) $\AA$ and O-Ca-O=119.14(4)$^{\circ}$; Tl-O=2.70(1) $\AA$ and O-Tl-O=92.38$^{\circ}$) and one $Tl^+$ ion occupies site II'. The remaining twelve $Tl^+$ ions are distributed over site III'. It appears that $Ca^{2+}$ ions prefer sites I and II in that order and $Tl^+$ ions occupy the remaining sites.

• Korean Chemical Engineering Research
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• v.47 no.4
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• pp.424-429
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• 2009

The effects of $Na_2O$, $SiO_2$ and $H_2O$ contents of the synthetic mixtures prepared from water glass on the crystallinity and crystallite size of sodalite were studied. The composition of the synthetic mixtures described by $x\;Na_2O{\cdot}y\;SiO_2{\cdot}Al_2O_3{\cdot}z\;H_2O$ was varied within x=2.5~7.5, y=1.4~3.0, z=140~400. The hydrothermal reaction was carried out at $140^{\circ}C$ for 2 days. High content of $Na_2O$ resulted in the high crystallinity and small crystallite of sodalite. The $SiO_2/Al_2O_3$ molar ratios of around 2 were suitable for the synthesis of sodalite, and produced zeolite species were varied by the $H_2O$ content. Sodalite was mainly obtained with a high crystallinity from the synthetic mixtures with $SiO_2/Al_2O_3$ molar ratio of around 2 and high content of $Na_2O$. The high content of sodium ions caused a decrease in the particle sizes because of their role of structure directing agent.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.135-142
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• 1989

Methyl tert-butyl ether(MTBE) was synthesized from vapor phase reaction of methanol with iso-butylene over HZSM-5 catalysts, and effects of SiO$_2/Al_2O_3$ ratio in the HZSM-5 catalysts and reaction conditions on products distribution have been examined. Acid strength and acid type of each catalyst with different SiO$_2/Al_2O_3$ ratio were measured using pyridine adsorption followed by temperature programmed desorption(TPD) and IR analysis. Reactants and products adsorption characteristics on different acid sites have also been examined. As the SiO$_2/Al_2O_3$ ratio of HZSM-5 catalyst was increased, selectivity to MTBE was improved as a result of decrease in dimethylether(DME) formation at the strong acid sites. Conversion and selectivity to MTBE were also greatly enhanced as $i-C_4H_8/CH_3OH$ reactant ratio was increased, and overall about 80$^{\circ}$C was adequate for the MTBE synthesis. The properties of deposited coke on spent catalysts were examined by TG, DTA and IR spectrum analysis, indicating the amount of the coke deposit in the order of HY > H-Mordenite > HZSM-5. Even if the coke deposited on H-Mordenite was little more in amount than to that on HZSM-5, the former deactivated quickly due to its non-interconnected channel structure. For HY, owing to its lange pore size, significant $i-C_4H_8$ polymerization was occured, and rapid deactivation and severe coke formation has resulted within few hours.