• Applied Chemistry for Engineering
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• v.19 no.4
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• pp.452-456
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• 2008

Mesoporous silicate materials have been used as adsorbents due to the advantage of high specific surface area and regular mesopores. In this study, conventional mesoporous silicates (MCM-41, and SBA-15) were utilized as adsorbents for gaseous benzene, one of volatile organic compounds. In the results of the breakthrough curves of gaseous benzene, SBA-15 showed a higher benzene adsorption capacity in adsorption condition of this study. Especially, compared to benzene adsorption of zeolite X, that of SBA-15 was higher by a factor of 2.7. With increasing adsorption temperature, adsorption capacity for benzene of SBA-15 was decreased rapidly. This indicates that benzene adsorbed weakly on SBA-15.

• KEPCO Journal on Electric Power and Energy
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• v.1 no.1
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• pp.115-120
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• 2015

$K_2CO_3$-based dry regenerable sorbents were prepared by spray-drying techniques to improve mass produced $K_2CO_3-Al_2O_3$ sorbents (KEP-CO2P, hereafter), and then tested for their $CO_2$ sorption capacity by a $2,000Nm^3/h$ (0.5 MWe) $CO_2$ capture pilot plant built for Unit 3 of the Hadong thermal power station in 2010. Each of the sample sorbents contained 35 wt.% $K_2CO_3$ as the active materials with various support materials such as $TiO_2$, MgO, Zeolite 13X, $Al_2O_3$, $SiO_2$ and hydrotalcite (HTC). Their physical properties and reactivity were tested to evaluate their applicability to a fluidized-bed or fast transport-bed $CO_2$ capture process. The $CO_2$ sorption capacity and percentage utilization of $K_2CO_3$-MgO based sorbent, Sorb-KM2, was $8.6g-CO_2/100g$-sorbents and 90%, respectively, along with good mechanical strength for fluidized-bed application. Sorbs-KM2 and KT were almost completely regenerated at $140^{\circ}C$. No degradation of Sorb-KM by $SO_2$ added as a pollutant in flue gas was observed during a cycle test.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.82-86
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• 1993

Two crystal structures of dehydrated $Ag_{3.3}Ca_{4.35}-A ({\alpha} = 12.256(2){\AA})$ and of its ethylene sorption complex (${\alpha} = 12.259(2){\AA}$) have been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m at 21(l)$^{\circ}$C. Both crystals were dehydrated at 360$^{\circ}$C and $2{\times}10^{-6}$ Torr for 2 days and one crystal was treated with 200 Torr of ethylene at 24(2)$^{\circ}$C. The structures were refined to final error indices, $R_1$=O.065 and $R_2$ = 0.088 with 202 reflections and $R_1$=0.049 and $R_2$ = 0.044 with 259 reflections, respectively, for which I>3${\sigma}$(I). In these structures, all Ag$^+$ and Ca$^{2+}$ ions are located on two and three different threefold axes associated with 6-ring oxygens, respectively. In $Ag_{3.3}Ca_{4.35}-A{\cdot}6.65\;C_2H_4,\;3.3\;Ag^+\;and\;3.35\;Ca^{2+}$ ions are recessed 1.09 ${\AA}$ and 0.21 ${\AA}$, respectively, into the large cavity from the (111) plane at O(3). Each Ag$^+$ and Ca$^{2+}$ ion in the large cavity forms a complex with one $C_2H_4$$^{2+}$ ions and ethylene molecules are longer than those between Ag$^+$ ions and ethylene molecules.

• Bulletin of the Korean Chemical Society
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• v.15 no.11
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• pp.940-944
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• 1994

The crystal structure of an ethylene sorption complex of dehydrated $Ag_{12}-A $reacted with bromine vapor has determined by single-crystal X-ray diffraction techniques in the cubic space group of Pm3m at 22(l)$^{\circ}$C (a=12.180(2) ${\AA}$). The crystal was prepared by dehydration of $Ag_{12}$-A at 400 $^{\circ}$C and $2 {\times} l0^{-6}$ Torr for 2 days, followed by exposure to 200 Torr of ethylene gas at 24(l) $^{\circ}$C for 1 hr. After the ethylene gas was evacuated for 1 hr, the crystal was exposed to 180 Torr of bromine vapor at 24(l) $^{\circ}$C for 1.5 h. The structure was refined to the final error indices, $R_1=0.066\;and\;R_2$ (weighted)=0.055, using 137 independent reflections for which I>3${\sigma}$I. About 55% of the sodalite unit contain two 6-ring $Ag^+$ ions and the remaining 45% contain $Ag_6$ molecules complexed to 2 $Ag^+$ ions at 6-ring sites to give $(Ag^+)_2(Ag_6).$ Upon sorption of ethylene, 4.75 ethylene molecules were sorbed per unit cell and of these, only 1.25 ethylene molecules were brominated by treatment of dibromine because of the limitation of the available space for the reaction products in the large cavity. In the large cavity, each of 3.5 $Ag^+$ ions forms a lateral ${\pi}$ complex with an ethylene molecule. About 2.5 8-ring $Ag^+$ ions per unit cell interact with 1.25 1,2-dibromoethane and each of ca. 1.25 6-ring $Ag^+$ ions also interacts with one of bromine atoms of 1,2-dibromoethane. Each bromine atom approaches a carbon atom with C-Br(l)=2.07(20) ${\AA}$ and C-Br(2)=2.07(10) ${\AA}$, respectively.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.3
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• pp.251-258
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• 2020

Single crystal of fully dehydrated and partially Ca²⁺-exchanged zeolites A (|Ca₄Na₄|[Si₁₂Al₁₂O₄₈]-LTA) was brought into contact with Se in fine pyrex capillary at 523 K for 5 days. Crystal structure of Se-sorbed |Ca₄Na₄|[Si₁₂Al₁₂O₄₈]-LTA has been determined by single-crystal X-ray diffraction techniques at 294 K in the cubic space group $Pm{\bar{3}}m$ (a = 12.2787(13) Å). The crystal structure of yellow |Ca₄Na₄Se₄|[Si₁₂Al₁₂O₄₈]-LTA has been refined to the final error indices of R₁/wR₂ = 0.0960/0.3483 with 327 reflections for which F_o > 4s(F_o). In this structure, 4 Na⁺ and 4 Ca²⁺ ions fill every 6-ring site: These ions are all found at three crystallographic positions, on 3-fold axes equipoints of opposite 6-rings. Selenium atoms are found at three crystallographically distinct positions: 2 Se atoms per unit cell at Se(1) are located opposite 6-rings in the sodalite cavity (Se(1)-Na(1) = 2.53(5) Å) and 1 at Se(2) opposite 4-rings (Se(2)-O(1) = 2.76(10) Å) and 1 at Se(3) opposite 6-rings in the large cavity (Se(3)-Na(1) = 2.48(5) Å). Two molecular of Se₂ (Se(1)-Se(1) = 2.37(7) or 2.90(8) Å and Se(2)-Se(3) = 2.91(5) ) Å) are found in all sodalite cavity and large cavity. Other clusters such as Se₄ and Se₈ could be existed in large cavity. The inter-selenium distances turned out to be longer that of gases Se₂ molecule.

• Journal of the Mineralogical Society of Korea
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• v.30 no.2
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• pp.45-57
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• 2017

Two single crystals of fully dehydrated $Cd^{2+}$-exchanged zeolites Y were prepared by the exchange of ${\mid}Na_{75}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$ ($Na_{75}-Y$, Si/Al = 1.56) with aqueous $0.05M\;Cd(NO_3)_2$ (pH = 3.65) at 294 K, followed by vacuum dehydration at 723 K (crystal 1) and a second crystal, similarly prepared, was exposed to zeolitically dried benzene for 72 hours at 294 K and evacuated (crystal 2). Their structures were determined crystallographically using synchrotron X-rays and were refined to the final error indices using $F_o$>$4{\sigma}(F_o)$ of $R_1/wR_2=0.040/0.121$ and 0.052/0.168, respectively. In crystal $1({\mid}Cd_{36}H_3{\mid}[Si_{117}Al_{75}O_{384}]-FAU)$, $Cd^{2+}$ ions primarily occupy sites I and II, with additional $Cd^{2+}$ ions at sites I', II', and a second site II. In crystal $2({\mid}Cd_{35}(C_6H_6)_{24}H_5{\mid}[Si_{117}Al_{75}O_{384}]-FAU)$, $Cd^{2+}$ ions occupy five crystallographic sites. The 24 benzene molecules are found at two distinct positions within the supercages. The 17 benzene molecules are found on the 3-fold axes in the supercages where each interacts facially with one of site IIa $Cd^{2+}$ ions. The remaining 7 benzene molecules lie on the planes of the 12-rings where each is stabilized by multiple weak electrostatic and van der Waals interactions with framework oxygens.

• 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.

• Korean Journal of Crystallography
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• v.8 no.1
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• pp.6-14
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• 1997

The crystal structures of $Sr_{31}K_{30}-X\;(Sr_{31}K_{30}Si_{100}A1_{92}O_{384};\;a=25.169(5) {\AA}$) and $Sr_{8.5}Tl_{75}-X (Sr_{8.5}Tl_{75}Si_{100}A1_{92}O_{384};\;a=25.041(5) {\AA}$) have been determined by single-crystal X-ray diffraction techniques in the cubic space group $\=F{d3}\;at\;21(1)^{\circ}C$. Each crystal was prepared by ion exchange in a flowing stream of aqueous $Sr(ClO_4)_2\;and\;(K\;or\;T1)NO_3$ whose mole ratio was 1 : 5 for five days. Vacuum dehydration was done at $360^{\circ}C$ for 2d. Their structures were refined to the final error indices $R_1=0.072\;and\;R_w=0.057$ with 293 reflections, and $R_1= 0.058\;and\;R_w=0.044$ with 351 reflections, for which $I>2{\sigma}(I)$, respectively. In dehydrated $Sr_{31}K_{30}-X,\;all\;Sr^{2+}$ ions and $K^+$ ions are located at five different crystallographic sites. Six-teen $Sr^{2+}$ ions per unit cell are at the centers of the double six-rings (site I), filling that position. The remaining 15 $Sr^{2+}$ ions and 17 $K^+$ ions fill site II in the supercage. These $Sr^{2+}$ and $K^+$ ions are recessed ca $0.45{\AA}\;and\;1.06{\AA}$ into the supercage, respectively, from the plane of three oxygens to which each is bound. ($Sr-O=2.45(1){\AA}\;and\;K-O=2.64(1){\AA}$) Eight $K^+$ ons occupy site III'($K-O=3.09(7){\AA}\;and\;3.11(10){\AA}$) and the remaining five $K^+$ ions occupy another site III'($K-O=2.88(7){\AA}\;and\;2.76(7){\AA}$). In $Sr_{8.5}Tl_{75}-X,\;Sr^{2+}\;and\;Tl^+$ ions also occupy five different crystallographic sites. About 8.5 $Sr^{2+}$ ions are at site I. Fifteen $Tl^+$ ions are at site I' in the sodalite cavities on threefold axes opposite double six-rings: each is $1.68{\AA}$ from the plane of its three oxygens ($T1-O=2.70(2){\AA}$). Together these fill the double six-rings. Another 32 $Tl^+$ ions fill site II opposite single six-rings in the supercage, each being $1.48{\AA}$ from the plane of three oxygens ($T1-O=2.70(1){\AA}$). About 18 $Tl^+$ ions occupy site III in the supercage ($T1-O=2.86(2){\AA}$), and the remaining 10 are found at site III' in the supercage ($T1-O=2.96(4){\AA}$).

• Korean Journal of Mineralogy and Petrology
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• v.35 no.3
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• pp.345-353
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• 2022

This study aimed to fundamentally understand changes of cell parameters of cation-exchanged mordenites using high resolution X-ray powder diffraction for studies that immobilization of various heavy metal cation using synthesis mordenite (Na_6.6Al_6.6Si_41.4O₉₆·20.4H₂O, Na-MOR). As a results of measurement by Thermogravimetric analysis (TGA), it was confirmed that 19.4, 20.4 water molecules per unit cell were present in monovalent-cation substituted MOR (Cs-MOR, Na-MOR), and 21, 23.1, 23.2 water molecules per unit cell were present in divalent-cation substituted MOR (Pb-MOR, Sr-MOR, Cd-MOR). The space group of all the samples were identified as Cmcm belonging to the orthorhombic crystal system. Compared to Na-MOR, starting material, relative peak intensity of (110) and (200) is significantly changed after cation substitution whereas peak position is almost similar. Also, (220) peak that was not found in Na-MOR was clearly observed in Pb-, Cd- and Sr-exchanged MOR. Thus, it was estimated that changes of atomic distribution usually occurred on ab-plane while changes of cell parameters were little. Detailed changes in the cell parameters of cation-exchanged mordenites were derived from whole profile fitting method using the GSAS suite program. Changes in the axial lengths and unit cell volume of cation substitution showed different relationship depending on ionic radius and charge number. In case of monovalent-cation substituted MOR, the length of a-axis increases whereas the length of b- and c-axis decrease by absorbed cation radius. In the case of divalent-cation exchanged MOR, the length of a-axis usually decreases while the length of b- and c-axis increases by cation radius. It was confirmed that unit cell volume of monovalent and divalent cation substituted MORs had an independent tendency by cation radius.