• Journal of the Korean Chemical Society
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• v.42 no.6
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• pp.607-617
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• 1998

Au was dosed on $TiO_2(001)$ film grown epitaxially on Mo(100) surface in about 90 ${\AA}$ thickness. The growth mode of Au, thermal behavior and stability of the Au clusters, and the binding energy shift of Au 4f with the change in the amount of Au loading were studied by Auger Electron Spectroscopy (AES), Temperature Programmed Desorption (TPD) spectroscopy, Ion Scattering Spectroscopy (ISS), and X-ray Photoelectron Spectroscopy (XPS). Au grows three dimensionally on $TiO_2(001)$ film and the average size of Au clusters prepared at low temperature is smaller than those at higher temperature and the size increases with temperature irreversibly. Au clusters on $TiO_2(001)/Mo(100)$ start evaporation at 1000 K. TPD spectra of Au show very asymmetric peaks with the same leading edges irrespective of the amount of Au loading. The temperature at the peak maximum increases with the amount of Au. The desorption energy of Au obtained from the leading edge analysis of the TPD spectra is about 50 kcal/mol. The initial sticking coefficient of Au on $TiO_2(001)$ is constant in the temperature range of 200-600 K. The binding energy of Au 4f for the Au loaded on the film less than 2.0 MLE shifts to higher energy compared with the bulk Au. The shift is +0.3 eV at 0.1 MLE Au amount.

• Bulletin of the Korean Chemical Society
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• v.28 no.4
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• pp.567-573
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• 2007

The crystal structure of ZnI2 molecule synthesized in zeolite A (LTA) has been studied by single-crystal X-ray diffraction techniques. A single crystal of |Zn6|[Si12Al12O48]-LTA, synthesized by the dynamic ion-exchange of |Na12|[Si12Al12O48]-LTA with aqueous 0.05 M Zn(NO3)2 and washed with deionized water, was placed in a stream of flowing 0.05 M KI in CH3OH at 294 K for four days. The resulting crystal structure of the product (|K6Zn3(KI)3(ZnI2)0.5|[Si12Al12O48]-LTA, a = 12.1690(10) A) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm3m. It was refined with all measured reflections to the final error index R1 = 0.078 for 431 reflections which Fo > 4σ (Fo). At four crystallographically distinct positions, 3.5 Zn2+ and nine K+ ions per unit cell are found: three Zn2+ and five K+ ions lie on the 3-fold axes opposite 6-rings in the large cavity, two K+ ions are off the plane of the 8-rings, two K+ ions are recessed deeply off the plane of the 8-rings, and the remaining a half Zn2+ ion lie on the 3-fold axes opposite 6-rings in the sodalite cavity. A half Zn2+ ion and an I- ion per unit cell are found in the sodalite units, indicating the formation of a ZnI2 molecule in 50% of the sodalite cavities. Each ZnI2 (Zn-I = 3.35(5) A) is held in place by the coordination of its one Zn2+ ion to the zeolite framework oxygens and by the coordination of its two I- ions to K+ ions through 6-rings (I-K = 3.33(8) A). Three additional I- ions per unit cell are found opposite a 4-ring in the large cavity and form a K3I2+ and two K2ZnI3+ ionic clusters, respectively.

• Bulletin of the Korean Chemical Society
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• v.26 no.2
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• pp.253-259
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• 2005

[$(tacn)_4Fe_4O_2(OH)_4]_2{\cdot}8Br{\cdot}9H_2O$ (tacn = 1,4,7-triazacyclononane), a tetranuclear iron(III) complex was synthesized by the hydrolysis of (tacn)FeCl3 and crystallizes in the orthorhombic space group, Pca2(1), with cell parameters, a = 37.574(3) $\AA$, b = 16.9245(12) $\AA$, c = 14.2830(11) $\AA$, V = 9082.9(12) ${\AA}^3$. [$(tacn)_4Fe_4O_2(OH)_4]^{4+}$ cations approach S4 point symmetry containing an adamantane skeleton. Four Fe(III) atoms have distorted octahedral environments with two hydroxo and an oxo bridges. Two [$(tacn)_4Fe_4O_2(OH)_4]^{4+}$ clusters having different Fe…Fe distances are connected to each other by the networked hydrogen bonds. The electrochemical behavior reveals irreversible three cathodic and two anodic peaks. Magnetic properties are characterized by antiferromagnetic (AF) interactions between Fe(III) ion spins. However, the low-lying states are still magnetic and exhibit a blocking behavior and a magnetic hysteresis at low temperatures.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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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 $(Cs_4)3^+\;and\;(Cs_6)4^+$.

• Journal of the Korean Electrochemical Society
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• v.15 no.1
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• pp.35-40
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• 2012

The composite membranes using Nafion as matrix and 1-ethyl-3-methylimidazolium tetracyanoborate (EMITCB) as ion-conducting medium in replacement of water were prepared and characterized. The amount of EMITCB in Nafion varied from 30 to 50wt%. The composite membranes are characterized by ion conductivity, thermogravitational analyses (TGA) and small-angle X-ray scattering (SAXS). The composite membranes containing EMITCB of 40wt% showed the maximum ionic conductivity which was ~0.0146 S $cm^{-1}$ at 423.15 K. It is inferred that the decrease in ionic conductivity of all the composite membranes might be due to the decomposition of a tetracyanoboric acid formed in the composite membranes. The results of SAXS indicated that the ionic clusters to conduct proton in the composite membranes were successfully formed. In accordance with the results of ionic conductivity as a function of a reciprocal temperature, SAXS showed a proportional decrease in scattering maximum $q_{max}$ as the amount of EMITCB increases in the composite membranes, which results in the increase in ionomer cluster size. The TGA showed no significant decomposition of the ionic liquid as well as the composite membranes in the range of operating temperature ($120-150^{\circ}C$) of high temperature proton exchange membrane fuel cells (HTPEMFC). As a result, EMITCB is able to play an important role in transferring proton in the composite membranes at elevated temperatures with no external humidification for proton exchange membrane fuel cells.

• Bulletin of the Korean Chemical Society
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• v.5 no.3
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• pp.117-121
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• 1984

The structure of $CS_{7.3}Ag_{4.7}Si_{12}Al_{12}O_{48}$, vacuum dehydrated zeolite A with all Na+ ions replaced by $Cs^+$ and $Ag^+$ as indicated, has been determined by single-crystal x-ray diffraction techniques in the cubic space group, Pm3m (a = 12.282 (1) ${\AA}$). The structure was refined to the final error indices $R_1$$R_2$ (weighted) = 0.099 using 347 independent reflections for whind intlch $I_0\;>\;3{\sigma}(I_0)$. Although deydration occurred at $360^{\circ}C$, no silver atoms or clusters have been observed. The 8-ring sites are occupied only by $Cs^+$ ion, and the 4-ring sites only by a single $Ag^+$ ion. The 6-ring sites contain $Ag^+$ and $Cs^+$ ions with $Ag^+$ nearly in 6-ring planes and $Cs^+$ well off them, one on the sodalite unit side. With regard to the 6-rings, the structure can be represented as a superposition of two types of unit cells: about 70 % have $4Ag^+$ and $4Cs^+$ ions, and the remaining 30 % have $3Ag^+$ and $5Cs^+$. In all unit cells, $3Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry; these ions are approximately 0.3 ${\AA}$ further from their nearest framework-oxygen neighbors than the sum of the appropriate ionic radii would indicate. To minimize electrostatic repulsions, the $Cs^+$ ions at Cs(1) are not likely to occupy adjacent 6-rings in the large cavity; they are likely to be tetrahedrally arranged when there are 4.

• Bulletin of the Korean Chemical Society
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• v.6 no.4
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• pp.202-206
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• 1985

The crystal structure of The crystal structure of $Ag^+$-Exchanged Zeolite A, $Ag_{4.6}Na_{7.4}-A$, dehydrated, treated with $H_2$, and evacuated, all at $350^{\circ}C$, has been determined by single crystal x-ray diffraction methods in the cubic space group Pm3m at $24(1)^{\circ}C;$ a = $12.208(2)\AA.$ The structure was refined to the final error indices R1 = 0.088 and R2 (weighted) = 0.069 using 194 independent reflections for which II_0$ > $3{\sigma}(I_0)$. On threefold axes near the centers of 6-oxygen rings, $7.4 Na^+$ ions and $0.6 Ag^+$ ions are found. Two non-equivalent 8-ring $Ag^+$ ions are found off the 8-ring planes, each containing about $0.6 Ag^+$ ions. Three non-equivalent Ag atom positions are found in the large cavity, each containing about 0.6 Ag atoms. This crystallographic analysis may be interpreted to indicate that $0.6 (Ag_6)^{3+}$ clusters are present in each large cavity. This cluster may be viewed as a nearly linear trisilver molecule $(Ag_3)^0$ (bond lengths, 2.92 and 2.94 $\AA;$ angle, $153^{\circ})$ stabilized by the coordination of each atom to a Ag^+$ ion at 3.30, 3.33, and 3.43 $\AA$, respectively. In addition, one of the silver atoms approaches all of the 0(1) oxygens of a 4-ring at $2.76\AA.$ Altogether $7.4 Na^+$ ions, $1.8 Ag^+$ ions, and 1.8 Ag atoms are located per unit cell. The remaining $1.0 Ag^+$ ion has been reduced and has migrated out of the zeolite framework to form silver crystallites on the surface of the zeolite single crystal.

• Bulletin of the Korean Chemical Society
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• v.29 no.10
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• pp.1983-1987
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• 2008

This study demonstrates the electrochemical conversion of the synthetic procedure of monolayer-protected clusters using a thin toluene layer over an edge plane pyrolytic graphite electrode. A thin toluene layer with a thickness of 0.31 mm was coated over the electrode and an immiscible liquid/liquid water/toluene interface was introduced. The transfer of the tetrachloroaurate ($AuCl_4^-$) ions into the toluene layer interposed between the aqueous solution and the electrode surface was electrochemically monitored. The $AuCl_4^-$ ions initially could not move through into the toluene layer, showing no reduction wave, but, in the presence of the phase transfer reagent, tetraoctylammonium bromide (TOABr), a cathodic wave at 0.23 V vs. Ag/AgCl was observed, indicating the reduction of the transferred $AuCl_4^-$ ions in the toluene layer. In the presence of dodecanethiol together with TOABr, a self-assembled monolayer was formed over the electro-deposited metallic gold surface. The E-SEM image of the surface indicates the formation of a highly porous metallic gold surface, rather than individual nanoparticles, over the EPG electrode.

• Polymer(Korea)
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• v.25 no.1
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• pp.90-97
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• 2001

Dispersions are prepared from poly(ethylene-co-acrylic acid) (PEAA) ionomer with two different counter-ions, ammonium and sodium. The diffusional characteristic of urea aqueous solution are measured for the films prepared from the above mentioned dispersions. It is attempted to find the relationship between diffusional behavior and various chemical and physical characteristics of films. DSC is employed to characterize glass transition temperature and degree of crystallinity and the structural features of crystal phase and ionic clusters are examined by WAXD and FTIR. The diffusional characteristics of ionomer is found to be dependent on various parameters such as the size of initial dispersion as well as the kind of counter ion and the degree of neutralization.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.11a
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• pp.9-10
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• 2005

We report on the fabrication and characterization of self- and artificially-controlled ZnO nanostructures have been investigated to establish nanostructure blocks for ZnO-based nanoscale device application. Systematic realization of self- and artificially-controlled ZnO nanostructures on $SiO_2/Si$ substrates was proposed and successfully demonstrated utilizing metalorganic chemical vapor deposition (MOCVD) in addition with a focused ion beam (FIB) technique. Widely well-aligned two-dimensional ZnO nanodot arrays ($4{\sim}10^4$ nanodots of 130-nm diameter and 9-nm height over $150{\sim}150{\mu}m^2$ with a period of 750 nm) have been realized by MOCVD on $SiO_2/Si$ substrates patterned by FIB. A low-magnification FIB nanopatterning mode allowed the periodical nanopatterning of the substrates over a large area in a short processing time. Ga atoms incorporated into the surface areas of FIB-patterned nanoholes during FIB engraving were found to play an important role in the artificial control of ZnO, resulting in the production of ZnO nanodot arrays on the FIB-nanopatterned areas. The nanodots evolved into dot clusters and rods with increasing MOCVD growth time.