• 제목/요약/키워드: Catalytic mechanism

검색결과 313건 처리시간 0.029초

Synthesis of Large Bumpy Silver Nanostructures with Controlled Sizes and Shapes for Catalytic Applications

  • Oh, Ju-Hwan;Kim, Do Yeon;Lee, Jae-Seung
    • Bulletin of the Korean Chemical Society
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    • 제35권4호
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    • pp.1001-1004
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    • 2014
  • We have synthesized disc-like large silver nanomaterials that have nanostructured bumps on the surface using smaller nanoplate seeds. The size and shape of the bumpy nanostructures are rationally controlled by changing the concentrations of nanoplate seeds, silver ion, reductant, and citrate ion. Importantly, the synthetic mechanism of these bumpy nanostructures is remarkably similar to that of the conventional seed-mediated growth based on tiny seeds. We have further investigated the catalytic properties of the bumpy nanostructures for the reduction of 4-nitrophenol, which is associated with a concomitant color change from yellow to colorless.

Reactions of Aryl Halides with Phenoxides and Alkoxides by Phase Transfer Catalysis

  • 조봉래;박성대
    • Bulletin of the Korean Chemical Society
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    • 제5권3호
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    • pp.126-129
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    • 1984
  • The reaction of aryl halides with phenoxides and alkoxides were investigated under phase transfer catalytic conditions. 2,4-Dinitro- and 4-nitrohalobenzenes reacted readily with phenoxides in NaOH(aq)-benzene in the presence of Bu4N+Br, affording the products quantitatively. Although the aryl halides did not react with alkoxides under the same condition, the reactions were completed within 2 hours at room temperature when conducted under solid-liquid phase transfenr catalytic condition. The reactivity of aryl halides was in the order, Ar = 2,4-dinitrophenyl > 4-nitrophenyl, and X = F > Cl, consistent with the SNAr mechanism. The reactivity of oxyanions increased with the change of reaction condition from liquid-liquid to solid-liquid phase transfer catalysis. The results were explained with the concentration and the degree of hydration of the anion in benzene.

Adsorption of Macrocyclic Cobalt Complex on a Glassy Carbon Electrode for the Electrocatalytic Reduction of $O_2$

  • 강찬
    • Bulletin of the Korean Chemical Society
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    • 제19권7호
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    • pp.754-760
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    • 1998
  • It was found that the adsorption of a cobalt(III) complex with a macrocyclic ligand, C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hmc), was induced on a glassy carbon electrode by heavily oxidizing the electrode surface. Adsorption properties are discussed. The glassy carbon electrode with the adsorbed complex was employed to see the catalytic activities for the electro-reduction of O2. In the presence of oxygen, reduction of (hmc)Co3+ showed two cathodic waves in cyclic voltammetry. Compared to the edge plane graphite electrode at which two cathodic waves were also observed in a previous study, catalytic reduction of O2 occurred in the potential region of the first wave while it happened in the second wave region with the other electrode. A rotating disk electrode after the same treatment was employed to study the mechanism of the O2 reduction and two-electron reduction of O2 was observed. The difference from the previous results was explained by the different reactivity of the (hmc)CoOOH2+ intermediate, which is produced after the two electron reduction of (hmc)Co3+ in the presence of O2.

저온에서 methane의 촉매적 열분해시 nanosized pyrolytic carbon whisker성장의 발견 (Growth of Nanosized Pyrolytic Carbon Whisker by Catalytic Pyrolysis of Methane)

  • H. S. Rhee;Park, Y. T.
    • 한국복합재료학회:학술대회논문집
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    • 한국복합재료학회 2003년도 춘계학술발표대회 논문집
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    • pp.173-175
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    • 2003
  • At the low temperature of $950^{\circ}C$ the $\mu\textrm{m}$-sized whisker growth during the catalytic CVD of pyrolytic carbon from methane with $H_2$- and Ar-gas on quartz substrate with NiO powder was found in this work. In the preliminary study it was observed from pure methane pyrolysis without catalyst at the high temperature $1500~1700^{\circ}C$. If the growth whisker should be stopped at initial stage, about 20 min. of the methane pyrolysis, it would be nanosized whisker growth. The screw growth mechanism and unique mechanical properties of whisker for composites were also recognized. If the pyrolysis would be continued, we could found also spiral growth of whistlers with diameter of about 1, 5 mm. The large length of whisker was about 10 cm in 20 minute.

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Sources, Components, Structure, Catalytic Mechanism and Applications: a Critical Review on Nicotinate Dehydrogenase

  • Zhi Chen;Xiangjing Xu;Xin Ju;Lishi Yan;Liangzhi Li;Lin Yang
    • Journal of Microbiology and Biotechnology
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    • 제33권6호
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    • pp.707-714
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    • 2023
  • Plant-derived insecticide-neonicotinoid insecticides (NIs) played a crucial role in the development of agriculture and food industry in recent years. Nevertheless, synthesis of these nitrogen-containing heterocyclic compounds with an effective and greener routing remains challenging especially to the notion raise of "green chemistry" and "atom economy". While bio-catalyzed methods mediated by nicotinate dehydrogenase (NDHase) then provide an alternative. The current review mainly focuses on the introduction of sources, components, structure, catalytic mechanism and applications of NDHase. Specifically, NDHase is known as nicotinic acid hydroxylase and the sources principally derived from phylum Proteobacteria. In addition, NDHase requires the participation of the electron respiratory chain system on the cell membrane. And the most important components of the electron respiratory chain are hydrogen carrier, which is mainly composed of iron-sulfur proteins (Fe-S), flavin dehydrogenase (FAD), molybdenum binding protein and cytochromes. Heterologous expression studies were hampered by the plasmid and host with high efficiency and currently only Pseudomonas entomophila L48 as well as Comamonas testosterone was successfully utilized for the expression of NDHase. Furthermore, it is speculated that the conjugate and inductive effects of the substituent group at position 3 of the substrate pyridine ring exerts a critical role in the hydroxylation reactions at position 6 concerning about the substrate molecular recognition mechanism. Finally, applications of NDHase are addressed in terms of pesticide industry and wastewater treatment. On conclusion, this critical review would not only deepen our understanding of the theory about NDHase, but also provides the guideline for future investigation of NDHase.

Steric and Electronic Effects of Tetradentate Nickel(II) and Palladium(II) Complexes toward the Vinyl Polymerization of Norbornene

  • Lee, Dong-Hwan;Lee, Jung-Hwan;Eom, Geun-Hee;Koo, Hyo-Geun;Kim, Cheal;Lee, Ik-Mo
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1884-1890
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    • 2011
  • A series of Ni(II) and Pd(II) complexes bearing N4-type tetradentate ligands, [Ni($X^1X^2$-6-$Me_2bpb$) 1] and [Pd($X^1X^2$-6-$Me_2bpb$) 2]; 6-$Me_2bpb$ = N,N'-(o-phenylene)bis(6-methylpyridine-2-carboxamidate), $X^1$ = Cl, H, or $CH_3$, $X^2$ = $NO_2$, Cl, F, H, $CH_3$, or $OCH_3$) were designed, synthesized, and characterized to investigate electronic and steric effects of ligand on the norbornene polymerization catalysts. Using modified methylaluminoxanes as an activator, the complexes exhibited high catalytic activities for the polymerization of norbornene and the nickel complexes exhibited better catalytic activity the palladium complexes. Ni complex 1a with $NO_2$ group on the benzene ring showed the highest catalytic activity of $4.9{\times}10^6$ g of PNBEs/$mol_{Ni}{\cdot}h$ and molecular weight of $15.28{\times}10^5$ g/mol with PDI < 2.30. Complexes with electron-withdrawing groups are more thermally stable (> 100 $^{\circ}C$), and tend to afford higher polymerization productivities than the ones having electron-donating groups. Amorphous polynorbornenes were obtained with good solubility in halogenated aromatic solvents. A vinyl addition mechanism has been proposed for the catalytic polymerization.

수소-알코올연료전지를 위한 금속-산화물 나노구조제어 (Control of Metal-Oxide Nanostructures for $H_{2}-Alcohol$ Fuel Cells)

  • 박경원;송유정;한상범;이종민
    • 한국신재생에너지학회:학술대회논문집
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    • 한국신재생에너지학회 2007년도 춘계학술대회
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    • pp.141-145
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    • 2007
  • Due to their excellent catalytic activity with respect to methanol oxidation on platinum at low temperature, platinum nanosized catalysts have been a topic of great interest for use in direct methanol fuel cells (DMFCs). Since pure platinum is readily poisoned by CO, a by-product of methanol electrooxidation, and is extremely expensive, a number of efforts to design and characterize Pt-based alloy nanosized catalysts or Pt nanophase-support composites have been attempted in order to reduce or relieve the CO poisoning effect. In this review paper, we summarize these efforts based upon our recent research results. The Pt-based nanocatalysts were designed by chemical synthesis and thin-film technology, and were characterized by a variety of analyses. According to bifunctional mechanism, it was concluded that good alloy formation with $2^{nd}$ metal (e.g., Ru) as well as the metallic state and optimum portion of Ru element in the anode catalyst contribute to an enhanced catalytic activity for methanol electrooxidation. In addition, we found that the modified electronic properties of platinum in Pt alloy electrodes as well as the surface and bulk structure of Pt alloys with a proper composition could be attributed to a higher catalytic activity for methanol electooxdation. Proton conducting contribution of nanosized electrocatalysts should also be considered to be excellent in methanol electrooxidation (Spillover effect). Finally, we confirmed the ensemble effect, which combined all above effects, in Pt-based nanocatalsyts especially, such as PtRuRhNi and $PtRuWO_{3}$, contribute to an enhanced catalytic activity.

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폴리카보네이트 용융중합 초기의 촉매기반 에스터 교환반응 동력학 (Catalyzed Transesterification Kinetics in Early Stage of Polycarbonate Melt Polymerization)

  • 정주연;이지목;홍성권;이진국;정현민;김용석
    • 폴리머
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    • 제39권2호
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    • pp.235-239
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    • 2015
  • 본 연구에서는 디올 단량체로서 바이오 유래 isosorbide 및 bisphenol A가 적용된 폴리카보네이트의 단일 및 공중합체를 얻기 위한 촉매로서 LiOH, $Cu(acac)_2$ 및 n-butyltin hydroxide oxide hydrate를 각각 적용하여 용융중합 초기 단계에서 에스터 교환반응의 동력학 분석을 실시하여 촉매활성도를 비교하였다. 단일 중합의 경우, $Cu(acac)_2$가 가장 큰 촉매활성도를 나타내었으나, 서로 다른 두 가지 디올 단량체가 적용된 용융 공중합의 경우에는 촉매의 적용 메커니즘 및 단량체의 화학구조에 의존하여 LiOH의 촉매활성이 가장 큼을 확인하였다. 이러한 연구결과는 최근 관심이 집중된 바이오 유래 친환경 폴리카보네이트용 촉매선정에 활용 가능함을 제시한다.

실리카라이트 폼에 담지된 MFI 제올라이트 촉매의 제조와 n-옥탄 분해반응에서 이들의 촉매 성질 (Preparation of MFI Zeolite Catalyst Supported on Silicalite Foam and Its Catalytic Property in the Cracking of n-Octane)

  • 정재식;최동배;송경근;하광;송요순;서곤
    • Korean Chemical Engineering Research
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    • 제43권4호
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    • pp.452-457
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    • 2005
  • 실리카라이트 폼에 $0.2{\mu}m$ 정도의 가는 MFI 제올라이트 입자를 담지하여 만든 폼(foam) 촉매에서 n-옥탄의 분해반응을 조사하였으며, 생성물 분포에 Delplot 기법을 적용하여 반응기구를 고찰하였다. 담지된 MFI 제올라이트의 Si/Al 몰비는 25로 추정되며, 담지량은 실리카라이트 폼의 25 wt%이었다. 겉보기 밀도는 $0.11g{\cdot}cm^{-3}$로 낮아 촉매 충전량을 0.02 g에서부터 0.5 g까지 바꿀 수 있어서 압력손실 없이 반응물과 생성물의 체류시간을 폭 넓게 조절하였다. 촉매 충전량이 많아지면 n-옥탄의 전환율과 올레핀 수율이 높아졌다. 촉매를 조금 사용하였을 때 생성물 분포는 단순하여 양성자 분해기구로 설명할 수 있었다. 촉매 사용량이 많아지면 분해 생성물의 추가 반응이 진행되어 반응성이 낮은 올레핀과 파라핀의 함량이 많아지며 생성물 분포가 복잡해졌다.

n-옥탄의 촉매 분해반응에서 제올라이트의 세공구조가 생성물 분포와 활성저하에 미치는 영향 (The Effect of Pore Structure of Zeolites on their Product Distribution and Deactivation in the Catalytic Cracking of n-Octane)

  • 민병구;이재열;송요순;서곤
    • Korean Chemical Engineering Research
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    • 제45권6호
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    • pp.547-553
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    • 2007
  • FER, MFI, MOR, BEA 제올라이트 촉매에서 n-옥탄의 분해반응을 양성자 분해반응(protolytic cracking mechanism) 기구로 해석하여 제올라이트의 세공구조가 생성물 분포와 활성저하에 미치는 영향을 고찰하였다. 세공이 작으면 분해반응이 많이 진행되어 $C_3$$C_3{^=}$가 주로 생성되나, 세공이 큰 제올라이트에서는 초기 생성물인 $C_4$$C_4{^=}$가 주로 생성된다. MFI 제올라이트에서는 탄소 침적이 억제되어 활성저하가 느리나, FER 제올라이트에서는 탄소가 많이 침적되어 촉매 활성이 빠르게 저하되었다. BEA 제올라이트에서는 탄소가 많이 침적되어도 활성저하가 느리나, MOR 제올라이트에서는 탄소가 조금만 침적되어도 활성저하가 빨랐다. n-옥탄 분해반응의 기구를 단순화하고 탄소 침적에 의한 세공 차폐 정도를 활성저하와 연관지어 반응시간에 따른 전환율 저하 과정을 모사하였다.