• 제목/요약/키워드: Transition metal catalyst

검색결과 123건 처리시간 0.021초

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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    • 제18권12호
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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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    • 제18권7호
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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.

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

  • 김영우;이주성
    • 공업화학
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    • 제4권4호
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    • pp.692-700
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    • 1993
  • 카본 담체에 백금과 전이금속과의 합금 촉매를 제조하여 촉매의 부식성, 촉매능 및 단전지에서의 전극성능을 전기화학적으로 비교 검토하였다. 그리고 합금촉매의 분석은 XRD로 확인하였다. 본 연구에서 제조된 여러 가지 백금 합금 촉매 중 Pt-Mo/carbon, Pt-Fe-Co/carbon 및 Pt-Fe/carbon 촉매가 보다 우수한 산소 환원 전류밀도를 나타내었으나 Pt-Mo/carbon 촉매의 경우 초기 전극전류의 대부분이 촉매의 부식에 의한 전류임을 확인할 수 있었다. Pt/carbon촉매를 사용하였을 경우 나타난 전극의 전류밀도는 $120mA/cm^2$이었으나 Pt-Fe-Co/carbon 의 경우는 $200mA/cm^2$으로 순수 백금촉매보다 우수한 전극성능을 나타내었다.

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

  • 장준원;김진환;배진영
    • 폴리머
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    • 제29권4호
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    • pp.338-343
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    • 2005
  • Chloride계 전이금속 촉매의 존재 하에서 ABS/PC/triphenyl phosphate 컴파운드의 열분해 거동을 TGA(thermogravimetric analysis)를 통해서 조사하였다. Chloiide계 전이금속 촉매(cobalt chloiide, ferric chloride, nickel chloride 및 zinc chloride)는 ABS/PC/triphenyl phosphate 컴파운드의 열분해 과정에서 화학반응을 야기하여, 질소분위기에서 숯(char) 형성이 관찰되었으며, $600^{circ}C$에서 $3\~l3\%$의 비휘발성 눈을 형성하였다. 이와 같은 질소분위기에서의 ABS/PC/triphenyl phosphate 컴파운드의 숯 생성은 chloride계 전이금속 촉매의 가교효과(crosslinking effect)로 추정된다. 한편, 공기분위기에서는 생성된 숯은 고온 산화반응에 의해서 역분해되었다.

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

  • 파시아 로즈 말디;김소희;이정숙;고영수
    • 공업화학
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    • 제27권3호
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    • pp.313-318
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    • 2016
  • 본 연구에서는 무정형 실리카의 세공 내를 아미노실란인 N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS)를 이용하여 표면 기능화한 후 표면 기능화된 실리카에 후전이 금속 촉매인 $(DME)NiBr_2$$PdCl_2$(COD)를 담지하여 노보넨 중합을 실시하였다. 중합 온도와 중합 시간, Al/Ni 몰비, 조촉매 종류를 변화시켜 중합 특성에 미치는 영향을 조사하였다. 담지되지 않은 촉매($(DME)NiBr_2$, $PdCl_2$(COD))로 노보넨 중합을 수행하였을 경우 중합반응은 일어나지 않았다. 그러나 조촉매로 MAO를 이용하여 중합한 경우 $SiO_2$/2NS/Ni 촉매는 중합 온도가 증가할수록 활성은 증가하였고 폴리노보넨(polynorbornene, PNB)의 분자량은 급격하게 감소하였다. $SiO_2$/2NS/Pd 촉매는 온도가 증가할수록 활성과 PNB의 분자량 모두 감소하는 경향을 보였다. $SiO_2$/2NS/Ni 촉매는 $SiO_2$/2NS/Pd 촉매보다 높은 온도에서 안정함을 확인하였다. 또한 두 촉매 모두 중합 시간이 길어질수록 노보넨의 전환율은 증가하였다. Al/Ni 몰비가 1000 : 1일 때 가장 높은 활성(15.3 kg-PNB/(${\mu}mol-Ni^*hr$))을 보이는 반면 가장 낮은 분자량($M_n$ = 124,000 g/mol)의 PNB를 합성하였다. 또한 조촉매로 Borate/TEAL을 이용하여 중합한 경우 $SiO_2$/2NS/Ni 촉매는 중합 온도가 증가할수록 활성과 분자량이 모두 감소하였다.

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

  • 김봉수;박영성
    • 대한환경공학회지
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    • 제29권4호
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    • pp.444-451
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    • 2007
  • 본 연구에서는 $\gamma-Al_2O_3$에 전이금속들을 함침시킨 촉매를 고정층 반응기에 충전시킨후 휘발성유기물질(VOCs)인 밴젠을 일정농도로 공급하면서 촉매산화 특성을 살펴보았다. 전이금속으로는 구리, 니켈, 망간, 철등을 포함해 8가지 금속을 선정하였고, 실험조건은 반응온도 $200\sim500^{\circ}C$, 벤젠의 농도 $1,000\sim3,000$ ppm, 공간속도 $5,000\sim60,000\;hr^{-1}$의 범위로 적용하였다. BET분석, 전자주사현미경(SEM), XRD분석을 통해 제조된 촉매의 물성을 조사하였으며, VOC 촉매산화반응의 전환율에 대하여 고찰하였다. 실험결과, VOC농도와 공간속도가 낮을수록 VOC산화반응의 전환율은 증가함을 알 수 있었다. 여러 전이금속촉매들 중에 Cu촉매가 벤젠에 대해 가장 높은 활성을 나타내었고, 소성온도 $500^{\circ}C$조건에서 전이금속의 함침율이 15 wt%일 경우 가장 높은 전환율을 나타내었다.

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

  • 신병길;이희수
    • 한국재료학회:학술대회논문집
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    • 한국재료학회 2011년도 추계학술발표대회
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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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저온형 연료전지용 산소의 고활성 환원 촉매 제조 (Preperation of catalyst having high activity on oxygen reduction)

  • 김영우;김형진;이주성
    • 한국에너지공학회:학술대회논문집
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    • 한국에너지공학회 1992년도 학술발표회 초록집
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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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    • 제18권4호
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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.

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

  • 김경일;김용성;홍태환
    • 한국수소및신에너지학회논문집
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    • 제21권2호
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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.