• Title/Summary/Keyword: transition metal catalyst

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Modification of Poly(methylsilene) Catalyzed by Group 4 and 6 Transition Metal Complexes and Its Pyrolysis

  • 양수연;박종목;우희권;김환기;김동표;황택성
    • Bulletin of the Korean Chemical Society
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    • v.18 no.12
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    • pp.1264-1268
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    • 1997
  • The poly(methylsilene) (1) was modified with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalyst and with the group 6 metal carbonyl M(CO)6 (M = Cr, Mo, W) catalyst, producing the highly cross-linked isoluble polymer and the lowly cross-linked soluble polymer, respectively. An interrelationship between molecular weight and percent ceramic residue yield with metal within the respective group was not found. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weight and lower percent ceramic residue yield than the polymers modified with the group 6 metal carbonyl catalysts do. The catalytic activity of group 4 metallocene combinations appears to be higher at ∼100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls. The pyrolysis of the modified 1 yielded SiC ceramic.

The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Alkali Metal Ethoxides with S-p-nitrophenyl 2-thiofuroate and 2-Thiophenethiocarboxylate in Absolute Ethanol

  • 엄익환;이윤정;남정현;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.18 no.7
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    • pp.749-754
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    • 1997
  • Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides (EtOM) with S-p-nitrophenyl 2-thiofuroate (1b) and 2-thiophenethiocarboxylate (2b) in absolute ethanol at 25.0±0.1 ℃. 1b is observed to be more reactive than 2b toward all the EtOM studied. The reactivity of EtOM is in the order EtOK > EtONa > EtO- > EtOLi for both substrates, indicating that K+ and Na+ behave as a catalyst while Li+ acts as an inhibitor in the present system. Equilibrium association constants of alkali metal ions with the transition state (KaTS) have been calculated from the known equilibrium association constants of alkali metal ion with ethoxide ion (Ka) and the rate constants for the reactions of EtOM with 1b and 2b. The catalytic effect (KaTS/Ka) is larger for the reaction of 1b than 2b, and decreases with decreasing the size of the alkali metal ions. Formation of 5-membered chelation at the transition state appears to be responsible for the catalytic effect.

Manufacture of Pt-transition Metal Alloy Catalyst for PAFC (PAFC용 합금 촉매 제조)

  • Kim, Yeong-Woo;Lee, Ju-Seong
    • Applied Chemistry for Engineering
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    • v.4 no.4
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    • pp.692-700
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    • 1993
  • Corrosivities and catalytic activities of platinum-transition metal alloy catalyses loaded on carbon substrate and were studied by electrochemical method using a unit cell. And the analysis of Pt-alloy catalyst was conducted by x-ray diffractometer. Among the catalysts, the Pt-Mo/carbon, Pt-Fe-Co/carbon and Pt-Fe/carbon catalyst showed more excellent cathodic current densities than others. It was found that most of cathodic current density for the Pt-Mo/carbon electrode was $120mA/cm^2$. The current density of the Pt-Fe-Co/carbon was much higher than that of Pt/carbon, reaching $200mA/cm^2$.

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Study on the Thermal Decomposition Behavior of[ABS/PC/Triphenyl Phosphate/Transition Metal Chloride] Compounds ([ABS/PC/Triphenyl Phosphate/Transition Metal Chloride] 컴파운드의 열분해 거동 연구)

  • Jang Junwon;Kim Jin-Hwan;Bae Jin-Young
    • Polymer(Korea)
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    • v.29 no.4
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    • pp.338-343
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    • 2005
  • The thermal degradation of ABS/PC/triphenyl phosphate compounds in the presence of transition metal chloride catalysts has been studied by thermogravimetric analysis (TGA). The reaction of transition metal chloride catalysts (cobalt chloride, ferric chloride, nickel chloride and zinc chloride) and ABS/PC/triphenyl phosphate compounds has been found to occur during the thermal degradation of the compounds. In a nitrogen atmosphere, char formation is observed, and $3\~13\%$of the reaction product is non-volatile at $600^{circ}$. The resulting enhancement of char formation in a nitrogen atmosphere has been explained as a catalytic crosslinking effect of transition metal chloride catalysts. On the other hand, transition metal chloride catalyzed char formation of ABS/PC/triphenyl phosphate compounds in air was unsuccessful due to the oxidative degradation of the char at a higher temperature.

Immobilization of Late Transition Metal Catalyst on the Amino-functionalized Silica and Its Norbornene Polymerization (아미노-기능화된 실리카 위 후전이 금속 촉매 담지 및 이를 이용한 노보넨 중합)

  • Pacia, Rose Mardie P.;Kim, So Hui;Lee, Jeong Suk;Ko, Young Soo
    • Applied Chemistry for Engineering
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    • v.27 no.3
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    • pp.313-318
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    • 2016
  • In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.

VOCs Oxidation Characteristics of Transition $Metals/\gamma-Al_2O_3$ Catalyst (전이금속/$\gamma-Al_2O_3$ 촉매의 VOCs 산화특성)

  • Kim, Bong-Soo;Park, Yeong-Seong
    • Journal of Korean Society of Environmental Engineers
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    • v.29 no.4
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    • pp.444-451
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    • 2007
  • Catalytic oxidation characteristics of benzene as a VOC was investigated using a fixed bed reactor system over transition $metals/\gamma-Al_2O_3$ catalysts. As transition metals, eight metals including copper, nickel, manganese, iron etc. were adopted. The parametric tests were conducted at the reaction temperature range of $200\sim500^{\circ}C$, benzene concentration of $1,000\sim3,000$ ppm, and space velocity range of $5,000\sim60,000\;hr^{-l}$. The property analyses such as BET, SEM, XRD and the conversions of catalytic oxidation of VOC were examined. The experimental results showed that the conversion was increased with decreasing VOC concentration and space velocity. It was also found that $Cu/\gamma-Al_2O_3$ catalyst calcinated at $500^{\circ}C$ showed the highest activity for the oxidation of benzene and 15% metal loading was the optimum impregnation level.

Thermal Stability of $MnOx-WO_3-TiO_2$ Catalysts Prepared by the Sol-gel Method for Low-temperature Selective Catalytic Reduction

  • Sin, Byeong-Gil;Lee, Hui-Su
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.10a
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    • pp.28.2-28.2
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    • 2011
  • The selective catalytic reduction (SCR) of NOx by $NH_3$ is well known as one of the most convenient, efficient, and economical method to prevent NOx emission in flue gas from stationary sources. The degradation of the reactivity is the obstacle for its real application, since high concentrations of sulfur dioxide and thermal factor would deactivate the catalyst. It is necessary to develop high stability of catalysts for low-temperature SCR. Among the transition metal oxides, $WO_3$ is known to exhibit high SCR activity and good thermal stability. The $MnOx-WO_3-TiO_2$ catalysts prepared by sol-gel method with various $WO_3$ contents were investigated for low-temperature SCR. These catalysts were observed in terms of micro-structure and spectroscopy analyses. The $WO_3$ catalyst as a promoter is used to enhance the thermal stability of catalyst since it increases the phase transition temperature of $TiO_2$ support. It was found that the addition of tungsten oxides not only maintained the temperature window of NO conversion but also increased the acid sites of catalyst.

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Preperation of catalyst having high activity on oxygen reduction (저온형 연료전지용 산소의 고활성 환원 촉매 제조)

  • 김영우;김형진;이주성
    • Proceedings of the Korea Society for Energy Engineering kosee Conference
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    • 1992.11a
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    • pp.39-40
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    • 1992
  • This paper dealt with the manufacturing of binary alloy catalyst and showed simple electrochemical method for determing catalytic activity of oxygen reduction in acid or alkaline electrolyte. The catalyst was prepared by impregnating transition metal salts on platinum or silver particles adsorbed before on carbon paper substrate. The electrochemical characteristics of the catalysts was investigated with carbon paper electrode or PTFE-boned porous electrode and then cathodic current densities and tafel slopes were compared. As a result, of all binary catalysts utilized in this work, Pt-Fe, Pt-Mo showed better oxygen reduction activity than pure platinum catalyst in acid electrolyte and Ag-Fe, Ag-Pt, and Ag-Ni-Bi-Ti catalyst did than pure silver catalyst in alkaline electrolyte. The current density of Pt-Fe electrode in acid electrolyte was one and half times higher than that of Pt electrode(~500mA/$\textrm{cm}^2$ at 0.7VvsNHE).

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Polymerization of Tetrahydrofuran with New Transition Metal Catalyst and Its Mechanism: (p- Methylbenzyl)- o -cyanopyridinium Hexafluoroantimonate

  • 강준원;한양규
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.433-438
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    • 1997
  • (p-Methylbenzyl)-o-cyanopyridinium hexafluoroantimonate, a new catalyst, was synthesized by the reaction of o-cyanopyridine with α-bromo-p-xylene followed by exchange of counteranion with SbF6θ. We examined the effect of the catalyst on the bulk polymerization of tetrahydrofuran under various conditions. The catalytic activity was best in the presence of 1 : 1 of epichlorohydrin used as cocatalyst versus catalyst concentration. The resulting polymers had relatively low conversions in 1.0-40%. Their number average molecular weights were in the range of 800 to 5300. Propagation rate increased with increase in temperature according to an Arrhenius expression giving an activation energy of 62 KJ/mol. We also found catalyst proceeds via a cationic mechanism.

Hydrogenation Properties on MgHx-Sc2O3 Composites by Mechanical Alloying (MgHx-Sc2O3 복합재료의 수소화 특성)

  • Kim, Kyeong-Il;Kim, Yong-Sung;Hong, Tae-Whan
    • Transactions of the Korean hydrogen and new energy society
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    • v.21 no.2
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    • pp.81-88
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    • 2010
  • Hydrogen energy applications have recognized clean materials and high energy carrier. Accordingly, Hydrogen energy applies for fuel cell by Mg and Mg-based materials. Mg and Mg-based materials are lightweight and low cost materials with high hydrogen storage capacity. However, commercial applications of the Mg hydride are currently hinder by its high absorption/desorption temperature, and very slow reaction kinetics. Therefore one of the most methods to improve kinetics focused on addition transition metal oxide. Addition to transition metal oxide in $MgH_x$ powder produce $MgH_x$-metal oxide composition by mechanical alloy and it analyze XRD, EDS, TG/DSC, SEM, and PCT. This report considers kinetics by transition metal oxide rate and Hydrogen pressure. In this research, we can see behavior of hydriding/dehydriding profiles by addition catalyst (transition metal oxide). Results of PCI make a excellent showing $MgH_x$-5wt.% Sc2O3 at 623K, $MgH_x$-10wt.% $Sc_2O_3$ at 573K.