• Title/Summary/Keyword: phase transfer catalyst

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Poly(ether-ester) Multiblock Copolymers Based on Poly(oxymethylene-alt-oxyalkylene) Glycols

  • Kim, Jin-Bong;Chun, Jae-Hwan;Kim, Dong-Hee;Park, Yun-Hee;Lee, Moo-Sung
    • Macromolecular Research
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    • v.10 no.4
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    • pp.230-235
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    • 2002
  • Alternating polyols of oxymethylene and oxyalkylene were synthesized and used as precursors for thermoplastic poly(ether-ester) elastomers (TPEs). The polyols were synthesized by reacting diols having different methylene units with dichloromethane in the presence of a phase transfer catalyst. The number of methylene units in the alkylene oxides was varied from 3 to 6. TPEs were prepared using the polyols as soft segments and poly(butylene terephthalate) units as hard segments. The polyols and TPEs synthesized were characterized using FTIR, NMR, GPC, DSC, and polarized optical microscopy. The polyols showed a profound odd-even effect on the melting (T$_{m}$) and glass transition temperatures (T$_{g}$). Polyols with odd numbers of methylene groups in the alkylene units have higher transition temperatures than polyols with odd number of methylene groups. The tendency is still kept in TPEs, even though the T$_{g}$ of soft segment in TPEs are slightly higher than those of corresponding neat polyols. The T$_{m}$ and T$_{g}$ of soft segments are almost constant in the range of 20 to 60 wt % contents of soft segments. On the other hand, the normalized heat of fusion of hard segment decreased with increasing the content of loft segment.ent.t.ent.

Heterogeneous Oxidation of Liquid-phase TCE over $CoO_x/TiO_2$ Catalysts (액상 TCE 제거반응을 위한 $CoO_x/TiO_2$ 촉매)

  • Kim, Moon-Hyeon;Choo, Kwang-Ho
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.3
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    • pp.253-261
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    • 2005
  • Catalytic wet oxidation of ppm levels of trichloroethylene (TCE) in water has been conducted using $TiO_2$-supported cobalt oxides at a given temperature and weight hourly space velocity. 5% $CoO_x/TiO_2$ might be the most promising catalyst for the wet oxidation at $36^{\circ}C$ although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Characterization of the $CoO_x$ catalyst by acquiring XPS spectra of both fresh and used Co surfaces gave different surface spectral features of each $CoO_x$. Co $2p_{3/2}$ binding energy of Co species exposed predominantly onto the outermost surface of the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $Co_2TiO_4$ and $CoTiO_3$. The spent catalyst possessed a 780.3 eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD measurements indicated that the phase structure of Co species in 5% $CoO_x/TiO_2$ catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

Numerical Study on Comparison of Serpentine and Parallel Flow Channel in High-temperature Proton Exchange Membrane Fuel Cells (고온형 고분자전해질형 연료전지에서의 사형 유로와 평행 유로 성능비교에 대한 수치해석적 연구)

  • AHN, SUNGHA;OH, KYEONGMIN;JU, HYUNCHUL
    • Transactions of the Korean hydrogen and new energy society
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    • v.29 no.1
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    • pp.41-55
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    • 2018
  • General polymer electrolyte fuel cell (PEMFC) operates at less than $80^{\circ}C$. Therefore liquid phase water resulting from electrochemical reaction accumulates and floods the cell which in turn increases the mass transfer loss. To prevent the flooding, it is common to employ serpentine flow channel, which can efficiently export liquid phase water to the outlet. The major drawback of utilizing serpentine flow channel is the large pressure drop that happens between the inlet and outlet. On the other hand, in the high temperature polymer electrolyte fuel cell (HT-PEMFC), since the operating temperature is 130 to $180^{\circ}C$, the generated water is in the state of gas, so the flooding phenomenon is not taken into consideration. In HT-PEMFCs parallel flow channel with lower pressure drop between the inlet and outlet is employed therefore, in order to circulate hydrogen and air in the cell less pumping power is required. In this study we analyzed HT-PEMFC's different flow channels by parallel computation using previously developed 3-D isothermal model. All the flow channels had an active area of $25cm^2$. Also, we numerically compared the performance of HT-PEMFC parallel flow channel with different manifold area and Rib interval against the original serpentine flow channel. Results of the analysis are shown in the form of three-dimensional contour polarization curves, flow characteristics in the channel, current density distribution in the Membrane, overpotential distribution in the catalyst layer, and hydrogen and oxygen concentration distribution. As a result, the performance of a real area fuel cell was predicted.

Continuous Wet Oxidation of TCE over Supported Metal Oxide Catalysts (금속산화물 담지촉매상에서 연속 습식 TCE 분해반응)

  • Kim, Moon Hyeon;Choo, Kwang-Ho
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.206-214
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    • 2005
  • Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

Silver nanowires and nanodendrites synthesized by plasma discharge in solution for the catalytic oxygen reduction in alkaline media

  • Kim, Hoe-Geun;Song, Myeon-Gyu;Kim, Dong-U;Lee, Sang-Yul
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.62-62
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    • 2018
  • Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

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An Analysis of Characteristics for the Non-catalytic Esterification of Palm Fatty Acid Distillate (PFAD) (팜지방산 디스틸레이트의 무촉매 에스테르화 반응특성 연구)

  • Hong, Seok Won;Cho, Hyun Jun;Yeo, Yeong-Koo
    • Korean Chemical Engineering Research
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    • v.52 no.3
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    • pp.395-401
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    • 2014
  • In this work, the reaction characteristics for the non-catalytic esterification of palm fatty acid distillate were analyzed. The esterification reaction was assumed as the pseudo homogeneous $2^{nd}$ order reversible reaction and 'reaction effectiveness factor (${\eta}$)' was used to take accounts into evaporation and reaction of water and methanol, which take place simultaneously in the liquid phase. The nonlinear programming was used to derive appropriate kinetic parameters, the reaction rate constant and mass transfer coefficient, minimizing the error between experimental data and the numerical values. Based on these parameters, the apparent activation energy was calculated to be 43.98 kJ/mol.

Thermal and Electrical Properties of PS/MWCNT Composite Prepared by Solution Mixing: Effect of Surface Modification of MWCNT (Solution Mixing법에 의한 PS/MWCNT 복합재료의 열 및 전기전도 특성: MWCNT 표면 개질의 영향)

  • Park, Eun-Ju;Lee, Jeong-Woo;Jung, Dong-Soo;Shim, Sang-Eun
    • Elastomers and Composites
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    • v.45 no.1
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    • pp.17-24
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    • 2010
  • Herein, the effect of the dispersion uniformity of the multi-wall carbon nanotube (MWCNT) on the thermal and electrical conductivity of polystyrene (PS)/MWCNT composite was investigated. The PS/MWCNT composites were prepared by solution mixing from dispersions of various MWCNTs in PS/tetrahydrofuran (THF) solution. Three types of MWCNTs were used; pristine MWCNT, hydroxyl functionalized MWCNT, which was functionalized with $KMnO_4$ in the presence of a phase transfer catalyst at room temperature, and pristine MWCNT with BYK-9077 as a dispersant. It was found that the stable dispersion state of MWCNT in PS/THF solutions significantly improved the thermal and electrical conductivity of the ultimate composites. It is noted that the thermal and electrical conductivity of PS/3 wt% pristine MWCNT composite with BYK-9077 were about 9.4 and 30~50% higher than those of PS/3 wt% pristine MWCNT composite, respectively.

Optimum Ratio between Nafion and 20, 40 wt% Pt/C Catalysts for MEAs (20, 40 wt% Pt/C 촉매를 사용한 MEA제조에서 나피온의 최적비)

  • Jung, Ju-Hae;Jung, Dong-Won;Kim, Jun-Bom
    • Journal of the Korean Electrochemical Society
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    • v.14 no.1
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    • pp.50-55
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    • 2011
  • To enhance the performance of a MEA (membrane electrode assembly) in a polymer electrolyte membrane fuel cell (PEMFC), optimum contents of Nafion ionomer as electrolyte in the 20 and 40 wt% Pt/C used in electrodes were examined. Variety characterization techniques were applied to examine optimum Nafion contents: cell performance test, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). According to Pt wt% supported on carbon support, it has been observed that polarization, ohmic, and mass transfer resistances were changed so that the cell performance was significantly dependent on the content of Nafion ionomer. Optimum Nafion ionomer contents in the 20 wt% Pt/C and 40 wt% Pt/C were showed 35 wt% and 20 wt%, respectively. This is due to different surface area of the Pt/C catalyst, and formation of triple phase boundary seems to be affected by the Nafion contents.

Surface Characteristics and Photocatalytic Propertiy of B Doped TiO2 Layer Synthesized by Plasma Electrolytic Oxidation Process (Plasma Electrolytic Oxidation 방식으로 제조된 B Doped TiO2의 표면특성과 광촉매 특성)

  • Lee, Jong-Ho;Lee, Young-Ki;Kim, Young-Jig;Oh, Han-Jun
    • Korean Journal of Materials Research
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    • v.31 no.10
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    • pp.552-561
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    • 2021
  • For the purpose of manufacturing a high efficiency TiO2 photocatalyst, B-doped TiO2 photocatalysts are synthesized using a plasma electrolytic oxidation method in 0.5 M H2SO4 electrolyte with different concentrations of H3BO3 as additive. For the B doped TiO2 layer fabricated from sulfuric electrolyte having a higher concentration of H3BO3 additive, the main XRD peaks of (101) and (200) anatase phase shift gradually toward the lower angle direction, indicating volume expansion of the TiO2 anatase lattice by incorporation of boron, when compared with TiO2 layers formed in sulfuric acid with lower concentration of additive. Moreover, XPS results indicate that the center of the binding energy peak of B1s increases from 191.45 eV to 191.98 eV, which suggests that most of boron atoms are doped interstitially in the TiO2 layer rather than substitutionally. The B doped TiO2 catalyst fabricated in sulfuric electrolyte with 1.0 M H3BO3 exhibits enhanced photocurrent response, and high efficiency and rate constant for dye degradation, which is ascribed to the synergistic effect of the new impurity energy band induced by introducing boron to the interstitial site and the improvement of charge transfer reaction.