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Polypyrrole Doped with Sulfonate Derivatives of Metalloporphyrin: Use in Cathodic Reduction of Oxygen in Acidic and Basic Solutions

  • 송위환;백운기
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.183-188
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    • 1998
  • Incorporation of metalloporphyrins into polypyrrole (PPy) film was achieved either by electropolymerization of pyrrole in the presence of metal-tetra(sulfonatophenyl)porphyrin anion (MTSPP, M=Co, Fe) or by metalizing hydrogenated tetra(4-sulfonatophenyl)porphyrin anion (H2TSPP) doped into PPy through ion-exchange. Electrochemical reduction of oxygen on the PPy doped with metallo porphyrin (PPy-MTSPP) was studied in acidic and basic solutions. Oxygen reduction on PPy-MTSPP electrodes appeared to proceed through a 4-electron pathway as well as a 2-electron path. In acidic solutions, the overpotential for O2 reduction on PPy-CoTSPP electrode was smaller than that on gold by about 0.2 V. In basic solutions the overpotential of the PPy-CoTSPP electrode in the activation range was close to those of Au and Pt. The limiting current was close to that of Au. However, polypyrrole doped with cobalt-tetra(sulfonatophenyl)porphyrin anion (PPy-CoTSPP) or with iron-tetra(sulfonatophenyl)porphyrin anion (PPy-FeTSPP) was found to have limited potential windows at high temperatures (above 50 ℃), and hence the electrode could not be held at the oxygen reduction potentials in basic solutions (pH 13) without degradation of the polymer.

Metallorganic Chemical Vapor Deposition and Characterization of TiO2 Nanoparticles

  • Jung, Oh-Jin;Kim, Sam-Hyeok;Cheong, Kyung-Hoon;Li, W.;Saha, S. Ismat
    • Bulletin of the Korean Chemical Society
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    • v.24 no.1
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    • pp.49-54
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    • 2003
  • TiO₂nanoparticles were synthesized using the metallorganic chemical vapor deposition process. Particles with and without metal ion dopants were obtained. X-ray photoelectron and energy dispersive X-ray spectroscopic measurements confirmed the stoichiometry of the TiO₂nanoparticles. X-ray diffraction patterns showed a polycrystalline anatase structure of TiO₂. Transmission electron microscopy revealed that these particles are of nanoscale dimensions. Exact particle size and size distribution analyses were carried out by dynamic light scattering. The average particle size was determined to be 22 nm. The nanosize particles provided large surface area for photocatalysis and a large number of free surface-charge carriers, which are crucial for the enhancement of photocatalytic activity. To improve the photocatalytic activity, metal ions, including transition metal ions $(Pd^{2+},\;Pt^{4+},\;Fe^{3+})$ and lanthanide ion $(Nd^{3+})$ were added to pure TiO₂nanoparticles. The effects of dopants on photocatalytic kinetics were investigated by the degradation of 2-chlorophenol under an ultraviolet light source. The results showed that the TiO₂nanoparticles with the metal ion dopants have higher photocatalytic activity than undoped TiO₂. The $Nd^{3+}$ ion of these dopant metal ions showed the highest catalytic activity. The difference in the photocatalytic activity with different dopants is related to the different ionic radii of the dopants.

A Study on Prediction Model of Chloride ion Permeation of Cement Mortar by Steel Powder (염해환경에서의 염화물이온 침투 예측에 관한 연구)

  • Kim, Jeong-Jin;Park, Soon-Jeon;Ko, Joo-Hwan;Han, Cheon-Goo
    • Proceedings of the Korea Concrete Institute Conference
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    • 2008.04a
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    • pp.513-516
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    • 2008
  • In this study the prediction model of Chloride Ion progress rate of concrete using steel powder as an addition is developed, in which the reduction of not only the diffusion rate of $Cl^-$ but also the corrosion rate by replenishment of pore by corrosion products. The model is based on the diffusions of $Cl^-$ and its reaction with $Fe^{2+}$, in chloride attack progression region. The model can also explain the characteristics of chloride ion permeation resistance of concrete that the matrix is densified due to corrosion products. The prediction by the model agreed well the experimental data in which the concrete using steel powder, and it showed the lower rate in long-term age to Chloride Ion progress rate than the concrete without steel powder. Consequently the model can predict Chloride Ion progress rate of concrete exposed in the atmosphere regardless of the water-to-cement raito, the amount of the content of steel powder, etc.

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Effect of Anode Voltage on Diamond-like Carbon Thin Film Using Linear Ion Source (Linear Ion Source를 이용한 Anode Voltage 변화에 따른 DLC 박막특성)

  • Kim, Wang-Ryeol;Jung, Uoo-Chang;Jo, Hyung-Ho;Park, Min-Suk;Chung, Won-Sub
    • Journal of Surface Science and Engineering
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    • v.42 no.4
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    • pp.179-185
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    • 2009
  • Diamond-like carbon(DLC) films were deposited by linear ion source(LIS)-physical vapor deposition method changing the anode voltages from 800 V to 1800 V, and characteristics of the films were investigated using residual stress tester, nano-indentation, micro raman spectroscopy, scratch tester and Field Emission Scanning Electron Microscope(FE-SEM). The results showed that the residual stress and hardness increased with increasing the ion energy up to anode voltage of 1400 V. It was also found that the content of $SP^3$ carbon increased with increasing the anode voltage $SP^3/SP^2$ ratio through investigation of $SP^3/SP^2$ ratio by the micro-raman analysis. From these results, it can be concluded that the physical properties of DLC films such as residual stress and hardness are increased with increasing the anode voltage. These results can be explained that 3-dimensional cross-links between carbon atoms and Dangling bond are enhanced and the internal compressive stress also increased with increasing the anode voltage. The optimal anode voltage is considered to be around 1400 V in these experimental conditions.

Abatement of Metal Ion Contents from Cotton Linter for the Manufacture of Regenerated Cellulose (방직용 재생섬유 제조를 위한 면 린터의 금속이온 함량 저감에 관한 연구)

  • Park, Hee Jeong;Son, Ha Neul;Choi, Jin Sung;Seo, Yung Bum
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.45 no.6
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    • pp.17-23
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    • 2013
  • The reduction of metal ion from the cotton linter for the preparation of NMMO (N-methylmorpholine N-oxide)-based dissolving pulp was investigated. The NMMO-based dissolving pulp was usually used for the manufacture of high quality fabrics, and need to have high alpha cellulose content and high brightness. NMMO, which is environmentally friendly, and reusable after recovering process, is very sensitive to the metal ions such as Cu, Fe, Mg, and Cr. Electron beam, sulfuric acid, acetic acid, and ozone treatment before bleaching were used and the concentration changes of the metal ions were compared to that of EDTA, a chelating agent. It was found that both acid treatments (sulfuric and acetic acid) were very effective and comparable to EDTA treatment at the same dosage in metal ion reduction, but electron beam and ozone treatment were not. The sulfuric acid treatment turned out to be effective in metal ion reduction, and most inexpensive.

Swelling at high radiation damage levels of 120 and 240 dpa in 3.5 MeV self-ion irradiated ferritic/martensitic steels

  • Myeongkyu Lee;Geon Kim;Sangjoon Ahn
    • Nuclear Engineering and Technology
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    • v.56 no.10
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    • pp.4115-4126
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    • 2024
  • The swelling behavior of ferritic/martensitic steels (FC92-B/-N, HT9, and Gr.92) was investigated following 3.5 MeV Fe++ ion irradiation. Tested alloys were helium-pre-implanted up to the peak contents of 120 and 240 appm with He/dpa ratio of 1 appm/dpa at room temperature and then exposed to self-ion beam to the peak damage conditions of 120 and 240 dpa at 475 ℃. Field-emission transmission electron microscopy was used to characterize the cavity evolution. FC92-B exhibited the highest resistance to swelling among the irradiated alloys. The final volumetric swelling of FC92-B reached 1.3 % at 70 dpa and 2.9 % at 140 dpa. On the other hand, HT9 exhibited the highest swelling, reaching 7.4 % at 140 dpa. Comparing the present swelling results at 140 dpa/140 appm He with swelling data at 280 dpa/280 appm He from our previous study, it was observed that Gr.92 and FC92-N swelled more at 140 dpa/140 appm He than at 280 dpa/280 appm He. This negative correlation between swelling and dose in Gr.92 and FC92-N is primarily attributed to the helium-associated swelling suppression at higher helium concentration of 280 appm. A bimodal cavity size distribution appeared only in Gr.92 and FC92-N at 280 dpa/280 appm. This result demonstrates that the excess amount of helium over 200 appm promoted early-stabilization of new-born cavities, resulting in preferentially enhanced cavity nucleation, while impeding the growth of nucleated cavities. An inhibition in cavity growth possibly led to an extended duration of nucleation-dominant stages, finally suppressing swelling in ion-irradiated Gr.92 and FC92-N alloys.

The Treatment of Heavy Metal-cyanide Complexes Wastewater by Zn$^{+2}$/Fe$^{+2}$ Ion and Coprecipitation in Practical Plant (II) (아연백법 및 공침공정을 이용한 복합 중금속-시안착염 폐수의 현장처리(II))

  • Lee, Jong-Cheul;Lee, Young-Man;Kang, Ik-Joong
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.5
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    • pp.524-533
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    • 2008
  • Industrial wastewater generated in the electroplating and metal finishing industries typically contain toxic free and complex metal cyanide with various heavy metals. Alkaline chlorination, the normal treatment method destroys only free cyanide, not complex metal cyanide. A novel treatment method has been developed which destroys both free and complex metal cyanide as compared with Practical Plant(I). Prior to the removal of complex metal cyanide by Fe/Zn coprecipitation and removal of others(Cu, Ni), Chromium is reduced from the hexavalent to the trivalent form by Sodium bisulfite(NaHSO$_3$), followed by alkaline-chlorination for the cyanide destruction. The maximum removal efficiency of chromium by reduction was found to be 99.92% under pH 2.0, ORP 250 mV for 0.5 hours. The removal efficiency of complex metal cyanide was max. 98.24%(residual CN: 4.50 mg/L) in pH 9.5, 240 rpm with 3.0 $\times$ 10$^{-4}$ mol of FeSO$_4$/ZnCl$_2$ for 0.5 hours. The removal efficiency of Cu, Ni using both hydroxide and sulfide precipitation was found to be max. 99.9% as Cu in 3.0 mol of Na$_2$S and 93.86% as Ni in 4.0 mol of Na$_2$S under pH 9.0$\sim$10.0, 240 rpm for 0.5 hours. The concentration of residual CN by alkaline-chlorination was 0.21 mg/L(removal efficiencies: 95.33%) under the following conditions; 1st Oxidation : pH 10.0, ORP 350 mV, reaction time 0.5 hours, 2nd Oxidation : pH 8.0, ORP 650 mV, reaction time 0.5 hours. It is important to note that the removal of free and complex metal cyanide from the electroplating wastewater should be employed by chromium reduction, Fe/Zn coprecipitation and, sulfide precipitation, followed by alkaline-chlorination for the Korean permissible limit of wastewater discharge, where the better results could be found as compared to the preceding paper as indicated in practical treatment(I).

The Study of Hyperfine Fields for Co0.9Zn0.1Cr1.9857Fe0.02O4 (Co0.9Zn0.1Cr1.9857Fe0.02O4 물질의 초미세자기장 연구)

  • Choi, Kang-Ryong;Kim, Sam-Jin;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.18 no.1
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    • pp.39-42
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    • 2008
  • [ $AB_2X_4$ ](A, B=Transition Metal, X=O, S, Se) are cubic spinel normal ferrimagnets, in which M ions occupy the tetrahedral sites and Cr ions occupy the octahedral sites. Recently, they have been investigated for behaviour of B site ions and A-B interaction. Polycrystalline $[Co_{0.9}Zn_{0.1}]_A[Cr_{1.98}{^{57}Fe_{0.02}}]_BO_4$ compound was prepared by wet-chemical process. The ferrimagnetic transition was observed around 90K. $M\"{o}ssbauer$ absorption spectra at 4.2K show that the well-developed two sextets are superposed with small difference in hyperfine fields($H_{hf}$). The hyperfine fields of $CoCr_{1.98}{^{57}Fe_{0.02}}O_4$ and $Co_{0.9}Zn_{0.1}Cr_{1.98}{^{57}Fe_{0.02}}O_4$ were determined to be 488, 478 kOe and 486, 468 kOe, respectively. We notice that the one of the magnetic hyperfine field values changes with Zn ion substitution. These results suggest the incommensurate states and spin-reorientation temperature($T_S=18K$) changes with Zn ions substitution below spin-reorientation temperature($T_S=28K$) of $CoCr_{1.98}{^{57}Fe_{0.02}}O_4$

Improvement of Electrochemical Performance of LiFePO4 by Carbon Coating and Morphology Control into Porous Structure (LiFePO4/C의 carbon coating 방법 및 다공성 구조 형성에 의한 전기화학적 특성 개선)

  • Kong, Ki Chun;Ju, Jeh Beck
    • Journal of the Korean Electrochemical Society
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    • v.17 no.4
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    • pp.229-236
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    • 2014
  • In this study, the method to improve the electrochemical performance of $LiFePO_4$ by carbon coating and morphology control into porous structure was studied. The synthesis of $LiFePO_4$ was done by coprecipitation method by two step procedure. In the first step $FePO_4$ precursor was synthesized by coprecipitation method, followed by impregnation of lithium into the precursor at $750^{\circ}C$. The carbon coating was done by both physical and chemical coating processes. Using the physical coating process, the amount of coating layer was 6% and the capacity achieved was 125 mAh/g. In case of chemical coating process, the active material delivered 130~140 mAh/g, which is about 40% improvement of delivered capacity compared to uncoated $LiFePO_4$. For the morphology control into porous structure, we added nano particles of $Al_2O_3$ or $SiO_2$ into the active materials and formed the nanocomposite of ($Al_2O_3$ or $SiO_2$)/$LiFePO_4$. Between them, $SiO_2/LiFePO_4$ porous nanocomposite showed larger capacity of 132 mAh/g.

Antioxidant Activity of Extract from Scutellaria baicalensis Georgi (황금 열수추출물의 항산화 작용에 대한 연구)

  • 이문조;오정석;박진우;김준기;최달영;김철호
    • Journal of Life Science
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    • v.10 no.3
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    • pp.236-240
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    • 2000
  • The purpose of this study was to investigate the antioxidant activity of the water extract from Scutellaria baicalensis Georgi. using linoleic acid as lipids. The extract exhibited antioxidative effect at all concentrations tested. With metal ion(Fe3+) present, the extract showed strong antioxidative effect. These result indicated that the extract can be used for antioxidative agents in oriental medicine.

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