• 제목/요약/키워드: Zeolite-Structure

검색결과 217건 처리시간 0.019초

Remarkable Structure Relaxation of Zeolite Windows in Rb₃- and K₃-A Crystal Structures of $M_3nA_{9-x}H_xSi_{12}Al_{12}O_{48}$ where M-Rb or K and x=1 or 0

  • 박종삼;윤명숙;임우택;김명철;서숭혁;허남호
    • Bulletin of the Korean Chemical Society
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    • 제16권10호
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    • pp.923-929
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    • 1995
  • Four crystal structures of M3-A (M3Na9-xHx-A, M=Rb or K and x=1 or 0), Rb3Na8H-A(a=12.228(1) Å and R1=0.046), Rb3Na9-A (a=12.258(3) Å and R1=0.058), K3Na8H-A (a=12.257(3) Å and R1=0.048) and K3Na9-A (a=12.257(3) Å and R1=0.052), have been determined by single crystal x-ray diffraction technique in the cubic space group Pm3^m at 21 ℃. In all structures, each unit cell contained three M+ ions all located at one crystallographically distinct position on 8-rings. Rb+ ions are 3.12 and 3.21 Å away respectively from O(1) and O(2) oxygens, about 0.40 Å away from the centers of the 8-rings, and K+ ions are 2.87 and 2.81 Å apart from the corresponding oxygens. These distances are the shortest ones among those previously found for the corresoponding ones. Eight 6-rings per unit cell are occupied by eight Na+ ions, each with a distance of 2.31 Å to three O(3) oxygens. The twelfth cation per unit cell is found as Na+ opposite 4-ring in the large cavities of M3Na9-A and assumed to be H+ for M3Na8H-A. With these noble non-framework cationic arrangements, larger M+ ions preferably on all larger 8-rings and the compact Na+ ions on all 6-rings, the bond angles in the 8-rings of M3-A, 145.1 and 161.0 respectively for (Si,Al)-O(1)-(Si,Al) and (Si,Al)-O(2)-(Si,Al), turned out to be remarkably stable and smaller, by more than 12 to 17°, than the corresponding angles found in the crystal structures of zeolites A with high concentration of M+ ions. It is to achieve these remarkably relaxed 8-rings, the main windows for the passage of gas molecules, with simultaneously maximized cavity volumes that M3-A have been selected as one of the efficient zeolite A systems for gas encapsulation.

Crystal Structures of Fully Dehydrated Zeolite $Cd_6-A$ and of $Rb_{13.5}-A$, the Product of its Reaction with Rubidium, Containing Cationic Clusters

  • Jang, Se-Bok;Kim, Yang;Seff, Karl
    • Bulletin of the Korean Chemical Society
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    • 제15권3호
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    • pp.236-241
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    • 1994
  • The crystal structures of $Cd_6-A$ evacuated at $2{\times}10^{-6}$ Torr and 750$^{\circ}$C (a=12.216(l) ${\AA}$), and of the product of its reaction with Rb vapor (a= 12.187(l) ${\AA}$), have been determined by single-crystal x-ray diffraction techniques in the cubic space group Pm$\bar{3}$m at 21(l)$^{\circ}$C. Their structures were refined to the final error indices, $R_1$=0.055 and $R_2$=0.067 with 191 reflections, and $R_1$=0.066 and $R_2$=0.049 with 90 reflections, respectively, for which I>3${\sigma}$(I). In dehydrated $Cd_6-A$, six $Cd^{2+}$ ions are found at two different threefold-axis sites near six-oxygen ring centers. Four $Cd^{2+}$ ions are recessed 0.50 ${\AA}$ into the sodalite cavity from the (111) plane at O(3), and the other two extend 0.28 ${\AA}$ into the large cavity from this plane. Treatment at 250 $^{\circ}$C with 0.1 Torr of Rb vapor reduces all $Cd^{2+}$ ions to give $Rb_{13.5^-}$A. Rb species are found at three crystallographic sites: three $Rb^+$ ions lie at eight-oxygen-ring centers, filling that position, and ca. 10.5 $Rb^+$ ions lie on threefold axes, 8.0 in the large cavity and 2.5 in the sodalite cavity. In this structure, ca. 1.5 Rb species more than the 12 $Rb^+$ ions needed to balance the anionic charge of zeolite framework are found, indicating that sorption of $Rb^0$ has occurred. The occupancies observed can be most simply explained by two "unit cell" compositions, $Rb_{12^-}A{\cdot}Rb$ and $Rb_{12^-}A{\cdot}2Rb$, of approximately equal population. In sodalite cavities, $Rb_{12^-}A{\cdot}Rb$ would have a $(Rb_2)^+$ cluster and $Rb_{12^-}A{\cdot}2Rb$ would have a triangular $(Rb_3)^+$ cluster. Each of the atoms of these clusters must bind further through a six-oxygen ring to a large cavity $Rb^+$ to give $(Rb_4)^{3+}$ (linear) and $(Rb_6)^{4+}$ (trigonal). Other unit-cell compositions and other cationic cluster compositions such as $(Rb_8)^{n+}$ may exist.

Two Crystal Structures of $Tl^+$ and $Zn^{2+}$ Exchanged Zeolite A, $Tl_{12-2x}Zn_x-A$ (x=4.3 and 3.25)

  • Mi Suk Jeong;Seong Hwan Song;Young Wook Han;Yang Kim
    • Bulletin of the Korean Chemical Society
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    • 제11권2호
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    • pp.150-154
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    • 1990
  • The structures of $Tl_{12-2x}Zn_x-A$ (x = 4.3 and 3.25), vacuum dehydrated zeolite A with all $Na^+$ ions replaced by $Tl^+$ and $Zn^{2+}$ as indicated, have been determined by single-crystal X-ray diffraction techniques in cubic space group Pm3m at 21(1) $^{\circ}C$ (a=12.100(2) ${\AA}$ for $Tl_{3.4}Zn_{4.3}-A$ and a=12.092(2) ${\AA}$ for $Tl_{5.5}Zn_{3.25}-A$). The crystals of $Tl_{3.4}Zn_{4.3}-A$ and $Tl_{5.5}Zn_{3.25}-A$ were prepared by flow method using exchange solutions in which mole ratios of $TlNO_3$,/TEX> and $Zn(NO_3)_2$ were 1:50 and 1:1, respectively, with total concentration of 0.05 M. The structures of the dehydrated $Tl_{3.4}Zn_{4.3}-A$ and $Tl_{5.5}Zn_{3.25}-A$ were refined to yield the final error indices $R_1$ = 0.075 and $R_2$ = 0.075 with 236 reflections, and $R_1$ = 0.057 and $R_2$ = 0.064 with 202 reflections, respectively, for which I > 3$\sigma$(I). Both structures indicate that Zn(II) ions are coordinated by three framework oxygens: the Zn(II) to O(3) distances are 2.08(1) ${\AA}$ for $Tl_{3.4}Zn_{4.3}-A$ and 2.07(1) ${\AA}$ for $Tl_{5.5}Zn_{3.25}-A$, respectively. In each structure, the angle subtended at Zn(II), O(3)-Zn(II)-O(3) is 119.9(3)$^{\circ}$ for $Tl_{3.4}Zn_{4.3}-A$, and 120.0(3)$^{\circ}$ for $Tl_{5.5}Zn_{3.25}-A$, respectively, close to the idealized trigonal-planar value. Zn(II) ions prefer to 6-ring sites. $Tl^+$ ions do not have any preference to a particular site but occupy simultaneously both at the 6-ring sites and 8-ring sites.

결정성 아날심(|Na0.94(H2O)|[Si2.06Al0.94O6]-ANA)의 합성 및 단결정구조: 양이온 및 물 분자의 위치, Si/Al 비의 결정 (Synthesis of Single Crystalline Analcime and Its Single-crystal Structure, |Na0.94(H2O)|[Si2.06Al0.94O6]-ANA: Determination of Cation Sites, Water Positions, and Si/Al Ratios)

  • 서성만;서정민;고성운;임우택
    • 대한화학회지
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    • 제55권4호
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    • pp.570-574
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    • 2011
  • 최대 0.20 mm 크기를 가진 아날심 단결정은 $3.00SiO_2$ : $1.50NaAlO_2$ : 8.02NaOH : $454H_2O$ : 5.00TEA의 겔 조성으로부터 합성되어졌다. $Na^+$ 이온으로 완전히 이온교환 된 아날심은 0.1 M 농도의 NaCl 수용액으로부터 준비하였다(이온교환용액의 pH는 NaOH 용액을 첨가하여 6에서 11로 맞추었다). $|Na_{0.94}(H_2O)|[Si_{2.06}Al_{0.94}O_6]-ANA(a=13.703(3){\AA})$의 분자식을 가지는 수화된 아날심 단결정의 구조는 294 K에서 Ibca의 orthorhombic 공간군으로 단결정 X-선 회절기법에 의해 결정되었다. 결정 구조의 최종 에러값은 $R_1/wR_2$= 0.054/0.143에 수렴되었다. 약 15개의 $Na^+$ 이온이 팔면체 배위로 3군데의 비동등한 위치에서 발견되었다. 합성된 아날심의 화학적 조성은 $Na_{0.94}(H_2O)Si_{2.06}Al_{0.94}O_6$ 확인되었으며, Si/Al 비는 단결정 구조 정밀화를 통하여 찾은 양이온의 점유수인 14.79개에 의해 2.19로 결정되었다.

Crystal Structure of Xenon Encapsulate within Na-A Zeolite

  • 임우택;박만;허남호
    • Bulletin of the Korean Chemical Society
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    • 제21권1호
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    • pp.75-80
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    • 2000
  • The positions of Xe atoms encapsulated in the molecular-dimensioned cavities of fully dehydrated Na-A have been determined. Na-A was exposed to 1050atm of xenon gas at 400 $^{\circ}C$ for seven days, followed by cooling at pressure to encapsulate Xe atoms. The resulting crystal structure of Na-A(7Xe) (a = 12.249(1) $\AA$, $R_1$ = 0.065, and $R_2$ = 0.066) were determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m at 21(1) $^{\circ}C$ and 1 atm. In the crystal structure of Na-A(7Xe), seven Xe atoms per unit cell are distributed over four crystallographically distinct positions: one Xe atom at Xe(1) lies at the center of the sodalite unit, two Xe atoms at Xe(4) are found opposite four-rings in the large cavity, and four Xe atoms, two at Xe(2) and others at Xe(3), respectively, occupy positions opposite and between eight- and six-rings in the large cavity. Relatively strong interactions of Xe atoms at Xe(2) and Xe(3) with $Na^+$ ions of four-, eight-, and six-rings are observed:Na(1)-Xe(2) = 3.09(6), Na(2)-Xe(3) = 3.11(2), and Na(3)-Xe(2) = 3.37(8) $\AA$. In each sodalite unit, one Xe atom is located at its center. In each large cavity, six Xe atoms are found, forming a distorted octahedral arrangement with four Xe atoms, at equatorial positions (each two at Xe(2) and Xe(3)) and the other two at axial positions (at Xe(4)). With various reasonable distances and angles, the existence of $(Xe)_6$ cluster is proposed (Xe(2)-Xe(3) = 4.78(6) and 4.94(7), Xe(2)-Xe(4) = 4.71(6) and 5.06(6), Xe(3)-Xe(4) = 4.11(3) and 5.32(4) $\AA$, Xe(2)-Xe(3)-Xe(2) = 93(1), Xe(3)-Xe(2)-Xe(3) = 87(1), Xe(2)-Xe(4)-Xe(2) = 91(4), Xe(2)-Xe(4)-Xe(3) = 55(2), 59(1), 61(1), and 68(1), and Xe(3)-Xe(4)-Xe(3) = 89($^{\circ}1$)). These arrangements of the encapsulated Xe atoms in the large cavity are stabilized by alternating dipoles induced on Xe(2), Xe(3), and Xe(4) by eight- and six-ring $Na^+$ ions as well as four-ring oxygens, respectively.

Synthesis of Zeolites ZSM-5 and ZSM-48 from Gasification Ashes of Agricultural Wastes

  • Lin, Kuen-Song;Lin, Wen-Chiang;Chitsan Lin
    • 대한전자공학회:학술대회논문집
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    • 대한전자공학회 2001년도 The 6th International Symposium of East Asian Resources Recycling Technology
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    • pp.610-615
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    • 2001
  • Over 800 thousand tons per year (TPY) agricultural biowastes, such as sugar cane bagasse, sugarcane leaf, rice straw, rice husk and corn leaf, are produced in Taiwan. These biomasses are the major types of agricultural wastes and are abundantly available. However, these biowastes cause disposal and landfill problems. Ossification ashes of the agricultural biowastes containing 70-95 % amorphous silica would make the utilization system of agricultural biowaste ashes become highly economically and environmentally attractive. Experimentally, high crystallinity (99%$^{+}$) zeolites ZSM-5 and ZSM-48 synthesized from the reaction mixtures containing a silica source from ashes of these biowastes gasification were investigated. Tetrapropylammonium bromide (TPABr) and 1,6-diamino-hexane (C$_{6}$ DN) were used as structure-directing agents in syntheses of ZSM-5 and ZSM-48, respectively. X-ray powder diffraction (XRD) and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDX) data indicated that ZSM-5 or ZSM-48 with a high crystallinity can be obtained within 48 hours of crystallization in the high pressure (15-20 atm) autoclave at 393-473 K. The Si/Al ratios of synthetic zeolite products were determined by X-ray fluorescence (XRF) and induced couple plasma/mass spectroscopy (ICP/MS). It was observed that the ZSM-5 crystals a.e composed of hexagonal rod-shaped crystals with typically 8-13 пm in size by SEM. In addition, ZSM-48 crystalline materials are composed of spherical aggregates of needle-shaped or rod-like crystals with typically 2-3 пm in diameter and 6-8 пm in length.h.

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증강현실을 이용한 문화재 콘텐츠 설계 및 구현 연구 (A Study of Design and Implementation of Cultural Property Contents Using Augmented Reality)

  • 서동희
    • 산업융합연구
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    • 제17권4호
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    • pp.15-20
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    • 2019
  • 증강현실은 카메라에 보인 현재 모습에, 중첩된 대상의 정보를 인지하는 방식으로 문화, 교육, 군사, 의료 등 다양한 분야에서 그 콘텐츠가 활용되고 있다. 특히 전시나 어린이 교육 콘텐츠는 이미 다양한 방식으로 제작되고 있다. 이러한 증강현실을 활용하여 문화재를 가상으로 구현하고 정보를 전달하는 콘텐츠를 개발하였다. '갈기비AR'과 '장영실의 발명품AR'을 통해 접근하기 어려운 문화재를 눈앞 가까이에서 경험 하도록 해준다. '갈기비AR'은 3D 블록 형태로 체험 콘텐츠를 제공함으로서 문화재 구조에 대해 손쉽게 알 수 있도록 한다. '장영실의 발명품AR'은 물체를 확대, 축소, 회전하며 함께 사진을 찍어 문화재를 보다 밀접하게 살펴볼 수 있도록 하였다. 바닥면을 인식하는 ARCore로 '갈기비 AR'는 증강된 화면 속에 비석을 위치하여 블록을 할 수 있게 한다. 측우기, 해시계, 물시계, 앙부일구를 손앞에 바로 보는 것과 같이 구현하여 체험자에게 사실감을 더 주고자 하였다. 문화재를 널리 알리기 위한 콘텐츠이며 문화재의 체험 콘텐츠를 통해 문화유산의 향유를 증대하고자 한다. 문화재 정보가 대중적으로 확산할 수 있도록 하는 데 제작되는 콘텐츠 기획에 도움이 되는 연구 자료이길 기대한다.

2차세공이 형성된 모더나이트와 알루미나를 혼합한 촉매상에서 Triphenylmethane의 분해반응 (Catalytic Cracking of Triphenylmethane on Alumina Mixed with Mordenite Formed Secondary Pore)

  • 이경환;최준우;하백현
    • 공업화학
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    • 제8권6호
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    • pp.1048-1053
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    • 1997
  • 수소형 모더나이트를 불화수소산처리하여 실리카/알루미나의 비가 다른 변형된 모더나이트를 만들고 이를 $\gamma$-알루미나와 혼합한 촉매를 제조하여 미소반응기에서 triphenylmethane (TPM)의 분해반응을 실시하였다. 미세공 구조인 수소형 모더나이트를 불화수소산처리로 탈알루미늄하면 산량은 감소하지만 2차 세공인 중세공이 형성되어 TPM의 분해활성과 2차 분해생성물인 벤젠의 선택성이 향상되었다. 그러나 더욱 불화수소산처리된 모더나이트는 산량 감소와 일부 세공구조의 파괴에 의한 미세공막힘 현상에 의해 분해활성이 저하되었다. 따라서 전처리된 모더나이트상에서 TPM의 분해활성과 벤젠의 선택성은 모더나이트의 실리카/알루미나 비가 17 정도에서 가장 우수하였다. 이들 전처리된 모더나이트를 알루미나와 혼합한 촉매는 순수한 모더나이트 촉매보다 TPM의 분해활성이 더욱 우수하였다. 이는 알루미나의 큰 중세공에서 TPM이 1차 분해반응하고 다음에 모더나이트의 중세공과 미세공에서 분해되는 단계적인 분해반응이 일어나기 때문이다.

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Synthesis and Characterization of Fe-Co/mesoHZSM-5 : Effect of Desilication Agent and Iron-cobalt Composition

  • Jimmy, Jimmy;Roesyadi, Achmad;Suprapto, Suprapto;Kurniawansyah, Firman
    • Korean Chemical Engineering Research
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    • 제58권1호
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    • pp.163-169
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    • 2020
  • Synthesis of Fe-Co/meso-HZSM5 catalyst, intended to be applied in Fischer-Tropsch (FT) reaction was investigated. The study emphasized the effect of desilication agents, NaOH and KOH, on the catalyst materials properties. Impregnation composition of active metal (Fe and Co) was also examined. HZSM-5, converted from ammonium ZSM-5 through calcination, was treated with NaOH and KOH for desilication, followed by impregnation with 10% metal loading. Fe composition in the initial mixture was varied at 10-50% from total composition. After impregnation, reduction was applied by flowing hydrogen gas at 400 ℃ for 10 hours. The use of KOH solution induced greater mesoporous volumes; however, it had a detrimental effect on zeolite crystal structure. NaOH solutions, on the other hand, increased mesopore area as high as 100%, indicated from surface area increase from 266.28 m2/g of HZSM-5, to 526.03 m2/g of NaOH-desilicated HZSM-5. In addition, the application of NaOH solution increased pore volume from 0.14 cc/g to 0.486 cc/g. Further, more Fe-Co alloys and less oxide of iron (Fe2O3) as well cobalt (Co3O4) had been commonly observed in the produced catalysts. The largest Fe-Co alloys could be found in 50Fe-50Co/HZSM-5

경북 청도군 유천화강암 내 제올라이트 광물군 스텔러라이트의 산출과 광물학적 특징 (Mineralogical Characteristics of Stellerite associated with the Yucheon Granite, Cheongdo, Korea)

  • 추창오;이진국;조현구
    • 한국광물학회지
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    • 제21권4호
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    • pp.365-372
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    • 2008
  • 스텔러라이트(stellerite)는 제올라이트 광물군에 속하는데 국내에서 이 광물의 산출은 매우 적으며 이에 관한 광물학적인 연구는 전무한 상황이다. 경북 청도군 유천화강암에서 산출하는 스텔러라이트는 길이 $3{\sim}4\;mm$, 폭 $1{\sim}2\;mm$의 등립질, 자형이 특징이며 약간 납작한 주상형태가 가장 흔하다. 결정의 집합체는 무작위방향이나 방사상으로 밀집하는 조직이 특징적이다. 스텔러라이트 결정은 c축을 따라 발달하는데 010면이 가장 넓고 길게 발달한다. 주사전자현미경(SEM)에 의한 미세조직관찰 결과에 따르면 스텔러라이트는 풍화작용이나 탈유리질화와 같은 변질작용을 겪었다. 스텔러라이트는 $161^{\circ}C$에서 가장 큰 탈수반응이 일어나고, $467^{\circ}C$에서의 탈수산기작용이 일어나며 그 이후에는 구조가 파괴된다. 스텔러라이트는 과냉각이 작은 환경에서 비교적 짧은 기간 동안에 잔류용액의 조성비가 비교적 일정하게 유지되는 환경에서 형성되었다.