• 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.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1125-1132
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• 2000

The pH effect of the precursor solution on the preparation of $LiCoO_2$ by a solution phase reaction containing malonic acid was carried out. Layered $LiCoO_2$ powders were obtained with the precursors prepared at the different pHs (4, 7, and 9) and heat-treated at $700^{\circ}C(LiCoO_2-700)$ or $850^{\circ}C(LiCoO_2-850)$ in air. pHs of the media for precursor synthesis affects the charge/discharge and electrochemical properties of the $LiCoO_2electrodes.$ Upon irrespective of pH of the precursor media, X-ray diffraction spectra recorded for $LiCoO_2-850$ powder showed higher peak intensity ratio of I(003)/I(104) than that of $LiCoO_2-700$, since the better crystallization of the former crystallized better. However, $LiCoO_2$ synthesized at pH 4 displayed an abnormal higher intensity ratio of I(003)/I(104) than those synthesized at pH 7 and 9. The surface morphology of the $LiCoO_2-850$ powders was rougher and more irregular than that of $LiCoO_2-700$ made from the precursor synthesized at pH 7 and 9. The $LiCoO_2electrodes$ prepared with the precursors synthesized at pH 7 and 9 showed a better electrochemical and charge/discharge characteristics. From the AC impedance spectroscopic experiments for the electrode made from the precursor prepared in pH 7, the chemical diffusivity of Li ions (DLi+) in $Li0.58CoO_2determined$ was 2.7 ${\times}$10-8 $cm^2s-1$. A cell composed of the $LiCoO_2-700$ cathode prepared in pH 7 with Lithium metal anode reveals an initial discharge specific capacity of 119.8 mAhg-1 at a current density of 10.0 mAg-1 between 3.5 V and 4.3 V. The full-cell composed with $LiCoO_2-700$ cathode prepared in pH 7 and the Mesocarbon Pitch-based Carbon Fiber (MPCF) anode separated by a Cellgard 2400 membrane showed a good cycleability. In addition, it was operated over 100 charge/discharge cycles and displayed an average reversible capacity of nearly 130 mAhg-1.

• Membrane Journal
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• v.32 no.6
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• pp.442-455
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• 2022

High-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) has been studied as an alternative to low-temperature PEMFC due to its fast activation of electrodes and high resistance to electrode poisoning by carbon monoxide. It is highly required to develop stable PEMs operating at high temperatures even doped by ion-conducting materials for the development of high-performance and durable HT-PEMFC systems. A number of studies have been conducted to develop polybenzimidazole (PBI)-based PEMs for applications in HT-PEMFC due to their high interaction with doped ion-conducting materials and outstanding thermomechanical stability under high-temperature operation. This review focused on the development of PBI-based PEMs showing high performance and durability. Firstly, the characteristic behavior of PBI-based PEMs doped with various ion-conducting materials including phosphoric acid was systematically investigated. And then, a comparison of the physicochemical properties of the PEMs according to the different membrane manufacturing processes was conducted. Secondly, the incorporation of porous polytetrafluoroethylene substrate and/or inorganic composites to PBI matrix to improve the membrane performances was studied. Finally, the construction of cross-linked structures into PBI-based PEM systems by polymer blending method was introduced to improve the PEM properties.

• Clean Technology
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• v.13 no.1 s.36
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• pp.54-63
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• 2007

Even traces of CO in the hydrogen-rich feed gas to proton exchange membrane fuel cells (PEMFC) poison the platinum anode electrode and dramatically decrease the power output. In this work, a variety of catalytic materials consisting of $Cu/Ce_xZr_{1-x}O_2$, (x = 0.0-1.0) were synthesised, characterized and tested for CO oxidation and preferential oxidation of CO (PROX). These catalysts prepared by hydrothermal and deposition-precipitation methods. The catalysts were characterized by XRD, XRF, SEM, BET, $N_2O$ titration and oxygen storage capacity (OSC) measurement. The effects of composition of the support and degree of excess oxygen were investigated fur activity and $CO_2$ selectivity with different temperatures. The composition of the support markedly influenced the PROX activity. Among the various $Cu/Ce_xZr_{1-x}O_2$ catalysts having different composition, $Cu/Ce_{0.9}Zr_{0.1}O_2$ and $Cu/Ce_{0.7}Zr_{0.3}O_2$ showed the highest activities (>99%) and selectivities (ca.50%) in the temperature range of $150{\sim}160^{\circ}C$. It was found that by using of $Ce_xZr_{1-x}O_2$ mixed oxide support which possesses a high oxygen storage capacity, oxidation-reduction activity of Cu-based catalyst was improved, which resulted in the increase of catalytic activity and selectivity of CO oxidation in excess $H_2$ environments.

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.78-83
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• 2014

In this research, we evaluated the performance and characteristics of carbon supported PtM (M = Ni and Y) alloy catalysts (PtM/Cs) synthesized by a modified polyol method. With the PtM/Cs employed as a catalyst for the oxygen reduction reaction (ORR) of cathodes in proton exchange membrane fuel cells (PEMFCs), their catalytic and ORR activities and electrical performance were investigated and compared with those of commercial Pt/C. Their particle sizes, particle distributions and electrochemically active surface areas (EAS) were measured by TEM and cyclic voltammetry (CV), while their ORR activity and electrical performance were explored using linear sweeping voltammetries with rotating disk electrodes and rotating ring-disk electrodes as well as PEMFC single cell tests. TEM and CV measurements show that PtM/Cs have the compatible particle size and EAS with Pt/C. When it comes to ORR activity, PtM/C showed the equivalent or better half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production(%) to or than commerical Pt/C. Based on results gained by the three electrode tests, when the PEMFC single cell tests were carried out, the current density measured at 0.6 V and maximum power density of PEMFC single cell adopting PtM/C catalysts were better than those adopting Pt/C catalyst. It is therefore concluded that PtM/C catalysts synthesized by modified polyol can result in the equivalent or better ORR catalytic capability and PEMFC performance to or than commercial Pt/C catalyst.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.261-272
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• 1992

Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.