• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• Journal of the Microelectronics and Packaging Society
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• v.24 no.4
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• pp.85-90
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• 2017

The $TiCl_4$ as a blocking material is adsorbed in the mesoporous $TiO_2$ electron transfer layer(ETL) of the Perovskite solar cell to prevent the direct contact between the FTO electrode and the photoactive layer(AL), and facilitate the movement of the electrons between $TiO_2:TiCl_4$ ETL and Perovskite AL to improve the photoelectric conversion efficiency(PCE). The structure of the perovskite solar cell is FTO/$TiO_2:TiCl_4$/Perovskite($CH_3NH_3PbI_3$)/spiro-OMeTAD/Ag. It was investigated that the dipping time of the $TiO_2$ into $TiCl_4$ aqueous solution affects on the photoelectric characteristics of the device. By the dipping for 30 minutes, the PCE of the perovskite solar cell with the $TiO_2:TiCl_4$ ETL was the highest 10.46%, which is 27% higher than the cell with $TiO_2$ ETL. From SEM, EDS, and XRD characterization on the $TiO_2:TiCl_4$ ETL and the perovskite AL, it was measured that the decrease of the porosity of the $TiO_2$ layer, the detection of the Cl component by the $TiCl_4$ adsorption, the cube-type morphology of perovskite AL, and shift of the $PbI_2$ peak of the perovskite AL. From these results, it was confirmed that the $TiO_2:TiCl_4$ ETL and the perovskite AL were formed.

• Journal of the Korean Chemical Society
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• v.4 no.1
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• pp.15-17
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• 1957

1. Preparation of Titanium tetrachloride; The following precesses were strictly followed as the preliminary step to obtain pure $TiOCl_2$, titanyl chloride; First, pure Titanium Oxide mixed with carbon is rolled into pills. After drying up perfectly, these pills are heated at 900∼1000${\circ}C$. And then the pills are subjected to the flow of $Cl_2$ gas in a quartz tube heated to 900-1000${\circ}C$. Thus Titanium tetrachloride is obtained. 2. Preparation of $TiOCl_2$ ; Yellowish trobrown solution is made by pouring 80 g of conc. HCl (sp.gr. 1.19) to 45 gr of Titanium tetrachloride (approx. 2 times of theoretical amount). Then this solution is kept settled for 5-days in a desiccator filled with phosphorous pentoxide at room temperature. As the colorless amorphous solid thus obtained is washed with aceton, 36.5 g of the pure salt are obtained. 3. Determination of composition. The analysis of the sample taken from the deposit desiccated gives the following data; (A) Qualitative analysis; a) $Ti(OH)_4$ is precipitated by adding NaOH in water solution of the salt. b) Adding $AgNO_3$ solution, the water solution of the salt gives white precipitate of AgCl. c) When acid and $H_2O_2$ are added, the solution turns its color to redish brown (This proves that $TiO^{++}$ was converted into $TiO^{++}$ by oxidation of $H_2O_2$. (B) Quantitative analysis; a) $Ti(OH)_4$ precipitated by $10{\%}$ NaOH isalitatsubjected consecutively to the filtration and ignition in porcelain crucible at approx. 1000${\circ}C$. , then $TiO_2$ thus formed is weighed and calculated into Ti content. b) Chlorine involved in water solution of the salt is determined by Vorhardt method. Result: The values obtained from previous analysis, devied by their atomic weight gives the following composition: Ti : Cl = 1 : 2 Therefore $TiOCl_2$ should be given as its molecular formula. 4. Summary. When $TiCl_4$ is additated into conc. HCl, $TiO^{++}$ formed exists as a stable form, and forms $TiOCl_2$. However $TiOCl_2$ is unstable to heating. When the temperature is raised to $65{\circ}C$the decomposition of the solution is accelerated, and gives $TiO_2$ aq. $TiOCl_2$ in addition is highly hygroscopic.

• Economic and Environmental Geology
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• v.29 no.6
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• pp.677-687
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• 1996

The Buckchang deposits which is located in the Ockcheon metamorphic zone, are emplaced along $N20-30^{\circ}E$ trending fissure sets. So it is a sort of fissure-filling ore deposits. The results of mineral paragenetic studies suggest two stages of hydrothermal mineralization; stage I: base-metal sulfides stage, stage II: late base-metal sulfides, electrum and silver-bearing sulfosalts stage. The silver-bearing sulfosalts occured as the Buckchang mine are mainly argentite and, minor of canfieldite, tetrahedrite, etc. Au:Ag ratios of the electrums show a highly limited range of nearly 1:1 in atomic %. The temperature, salinity and pressure of the Buckchang deposits estimated from fluid inclusion and sulfur isotope studies are as follows; stage I: $174{\sim}250^{\circ}C$, 0.35~4.01 NaCl eq. wt.%, 0.40~1.00 Kbar, stage II: $138{\sim}222^{\circ}C$, 1.9~8.4 NaCl eq. wt.%, 0.22~0.53 Kbar. The estimated oxygen and sulfur fugacity during stage I mineralization, based on phase relation of associated minerals, range from $10^{-39.7}{\sim}10^{-44.7}$ atm. and $10^{-13.4}{\sim}10^{-18.1}$ atm., respectively. All these evidences suggest that the Buckchang deposits are polymetallic epithermal ore deposits.

• Journal of Conservation Science
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• v.37 no.2
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• pp.179-189
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• 2021

In this study, the research objects are gilt plated silver-iron nails excavated from the west of the tombs in Neungsan-ri, Buyeo. A gilt plated silver-iron nail was fabricated by combining silver and iron via heating and then gilding amalgam on top of this combination, demonstrating that this ancient artifact that can be replicated using current technology. Since the metal (Au, Ag) surface of these gilt plated artifacts are covered with iron oxide, which slips into the cracks and scratches of the artifacts as well, desalination is essential. Based on the results of the preliminary experiment, the research objects were classified into grades A, B, and C, according to the degree of corrosion and then desalinated using an alkali solution (NaOH, Sodium Sesquicarbonate of 0.1 M) at 60℃. The results demonstrate that the more serious is the degree of corrosion, the more is the amount of Cl^- detected. Further, more Cl^- was released when NaOH was used than when sodium sesquicarbonate was used, for all grades except Grade A. Furthermore, the more serious is the degree of corrosion, the longer is the desalination period and the reaction with NaOH for all grades except Grade A. A comparison of the Fe composition of the surface before and after desalination shows that Fe composition is the use of NaOH resulted in a smaller increase compared with the use of sodium sesquicarbonate, for all grades except Grade B. However, four of the nails were damaged owing to NaOH (Grade B 3ea, Grade C 1ea) during desalination. Thus, Cl^- ions are more stably released when sodium sesquicarbonate is used than when NaOH is used.

• Economic and Environmental Geology
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• v.39 no.1 s.176
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• pp.9-25
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• 2006

Baekun gold-silver deposit is an epithermal quartz vein that is filling the fault zone within Triassic or Jurassic foliated granodiorite. Mineralization is associated with fault-breccia zones and can be divided into two stages. Stage I which can be subdivided early and late depositional stages is main ore mineralization and stage II is barren. Early stage I is associated with wallrock alteration and the formation of sulfides such as arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, stannite, galena. Late stage I is characterized by Au-Ag mineralization such as electrum, Ag-bearing tetrahedrite, stephanite, boulangerite, pyrargrite, argentite, schirmerite, native silver, Ag-Te-Sn-S system, Ag-Cu-S system, pyrite, chalcopyrite and galena. Fluid inclusion data indicate that homogenization temperatures and salinity of stage I range from $171.6^{\circ}C\;to\;360.8^{\circ}C\;and\;from\;0.5\;to\;10.2\;wt.\%\;eq.$ NaCl, respectively. It suggest that ore forming fluids were cooled and diluted with the mixing of meteoric water. Also, Temperature (early stage I: $236\~>380^{\circ}C,\;$ late stage $I: <197\~272^{\circ}C$) and sulfur fugacity (early stage $I:\;10^{-7.8}$ a atm., late stage I: $10^{-14.2}\~10^{-l6}atm$.) deduced mineral assemblages from stage 1 decrease with paragenetic sequence. Sulfur ($2.4\~6.1\%_{\circ}$(early stage $I=3.4\~5.3\%_{\circ},\;late\;stage\;I=2.4\~6.1\%_{\circ}$)), oxygen ($4.5\~8.8\%_{\circ}$(quartz: early stage $I=6.3\~8.8\%_{\circ}$, late stage $I=4.5\~5.6\%_{\circ}$)), hydrogen ($-96\~-70\%_{\circ}$ (quartz: early stage $I=-96\~-70\%_{\circ},\;late\;stage\;f=-78\~-74\%_{\circ},\;calcite:\;late\;stage\;I=-87\~-76\%_{\circ}$)) and carbon ($-6.8\~-4.6\%_{\circ}$ (calcite: late stage I)) isotope compositions indicated that hydrothermal fluids may be magmaticorigin with some degree of mixing of another meteoric water for paragenetic time.

• Journal of Electrochemical Science and Technology
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• v.14 no.1
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• pp.15-20
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• 2023

Ionic liquids are considered as a promising, alternative solvent for the electrochemical synthesis of metals because of their high thermal and chemical stability, relatively high ionic conductivity, and wide electrochemical window. In particular, their wide electrochemical window enables the electrodeposition of metals without any side reaction of electrolytes such as hydrogen evolution. The electrodeposition of silver is conducted in 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl) ionic liquid system with a silver source of AgCl. This study is the first attempt to electrodeposit silver nanoparticles without using co-solvents other than [C4mim]Cl. Pulse electrolysis is employed for the synthesis of silver nanoparticles by varying applied potentials from -3.0 V to -4.5 V (vs. Pt-quasi reference electrode) and pulse duration from 0.1 s to 0.7 s. Accordingly, the silver nanoparticles whose size ranges from 15 nm to ~100 nm are obtained. The successful preparation of silver nanoparticles is demonstrated regardless of the kinds of substrate including aluminum, stainless steel, and carbon paper in the pulse electrolysis. Finally, the antimicrobial property of electrodeposited silver nanoparticles is confirmed by an antimicrobial test using Staphylococcus aureus.

• Journal of Integrative Natural Science
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• v.2 no.1
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• pp.18-23
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• 2009

This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.

• Journal of Industrial Technology
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• v.39 no.1
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• pp.15-19
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• 2019

This work focused on characterization of the starch degradation activity from extremophile strain Deinococcus geothermalis. Glucoamylase gene from D. geothermalis was cloned and overexpressed by pET-21a vector using E. coli BL21 (DE3). In order to characterize starch degrading activity of recombinant glucoamylase, enzyme was purified using HisPur Ni-NTA column. The recombinant glucoamylase from D. geothermalis exhibited the optimum temperature as $45^{\circ}C$ for starch degradation activity. And highly acido-stable starch degrading activity was shown at pH 2. For further optimization of starch degrading activity with metal ion, various metal ions ($AgCl_2$, $HgCl_2$, $MnSO_4{\cdot}4H_2O$, $CoCl_2{\cdot}6H_2O$, $MgSO_4$, $ZnSO_4{\cdot}7H_2O$, $K_2SO_4$, $FeCl_2{\cdot}4H_2O$, NaCl, or $CuSO_4$) were added for enzyme reaction. As results, it was found that $FeCl_2{\cdot}4H_2O$ or $MnSO_4{\cdot}4H_2O$ addition resulted in 17% and 9% improved starch degrading activity, respectively. The recombinant glucoamylase from D. geothermalis might be used for simultaneous saccharification and fermentation (SSF) process at high acidic conditions.

• Journal of the Korean Chemical Society
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• v.37 no.5
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• pp.477-482
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• 1993

The determination of trace level mercury in bio-materials has been investigated by the square wave anodic stripping voltammetry (ASV)-technique at glassy carbon electrode. Prior to analysis, the bio-materials were digested with HNO3/H2SO4 mixture and KMnO4 was added to complete the oxidation. The detection limit of the mercury varied greatly with deposition time, deposition potential, pH and stirring rate. When deposition is carried out for 240 sec with 400 rpm stirring at -1.0 volts vs. Ag/AgCl, the detection limit was below $0.5\;ppb\;(2.5{\times}10^{-9} M)$. The method is recommended for trace level mercury analysis of biomaterials because this procedure is time saving and has higher sensitivity.