• Title/Summary/Keyword: Catalytic mechanism

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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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    • v.35 no.4
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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

  • Jo, Bong Rae;Park, Seong Dae
    • Bulletin of the Korean Chemical Society
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    • v.5 no.3
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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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    • v.19 no.7
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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.

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

  • H. S. Rhee;Park, Y. T.
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2003.04a
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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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    • v.33 no.6
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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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    • v.32 no.6
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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.

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

  • Park, Kyung-Won;Song, You-Jung;han, Sang-Beom;Lee, Jong-Min
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.06a
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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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Catalyzed Transesterification Kinetics in Early Stage of Polycarbonate Melt Polymerization (폴리카보네이트 용융중합 초기의 촉매기반 에스터 교환반응 동력학)

  • Jung, Ju Yeon;Lee, Ji Mok;Hong, Sung Kwon;Lee, Jin Kuk;Jung, Hyun Min;Kim, Yong Seok
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.235-239
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    • 2015
  • In this work, we evaluated catalytic activity of LiOH, $Cu(acac)_2$ and n-butyltin hydroxide oxide hydrate in the early stage of the melt transesterification of isosorbide and bisphenol A as diol monomers and diphenylcarbonate for the melt polymerizaiton of polycarbonate. $Cu(acac)_2$ proved to be the most active catalyst for homopolymerization process, while the catalytic activity of LiOH was higher than the others in case of melt copolymerization depending on the catalytic mechanism and chemical structure of catalyst. We suggested that evaluation of catalytic activity can be used for selection of catalyst system in bio-based copolymerization of polycarbonate.

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

  • Jung, Je Sik;Choi, Dong Bae;Song, Kyeong Keun;Ha, Kwang;Song, Yo Soon;Seo, Gon
    • Korean Chemical Engineering Research
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    • v.43 no.4
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    • pp.452-457
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    • 2005
  • Foam-type MFI zeolite catalyst was prepared by dispersing fine ($-0.2{\mu}m$) particles of MFI zeolite on silicalite foam. Catalytic cracking of n-octane was investigated over the foam-type catalyst and Delplot method was employed to interpret product compositions for deducing reaction mechanism. The Si/Al molar ratio of dispersed MFI zeolite was estimated 25 and its dispersed amount of silicalite foam was 25 wt%. Since the apparent density of the foam type catalyst was very low $0.11g{\cdot}cm^{-3}$, the catalyst loading amount could be varied from 0.02 g to 0.5 g without concerning pressure drop, providing a wide variance in the residence time of the reactants and products. The conversion and olefin yield in the catalytic cracking of n-octane increased with the catalyst loading. The product composition was very simple and could be explained by applying the protolytic cracking mechanism when the catalyst loading was small. Higher loading of the catalyst brought about further reactions of cracked products, accumulating lower olefin and paraffin with low reactivity in product stream and resulting in complex product composition.

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

  • Min, Byung Goo;Lee, Jae Youl;Song, Yo Soon;Seo, Gon
    • Korean Chemical Engineering Research
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    • v.45 no.6
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    • pp.547-553
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    • 2007
  • The catalytic cracking of n-octane over FER, MFI, MOR and BEA zeolites was studied by the protolytic cracking mechanism in order to understand the effect of pore structure of zeolites on their product composition and deactivation. The selectivities for $C_3$ and $C_3{^=}$ were high over the zeolites with medium pores due to additional cracking, while those for $C_4$ and $C_4{^=}$, the initial products, were high over the zeolites with large pores. MFI zeolite showed slow deactivation due to small carbon deposit, while FER zeolite with small pores deactivated rapidly with severe carbon deposit. The deactivation of BEA zeolite was slow even with a large amount of carbon deposit, but MOR zeolite showed a rapid deactivation even with a small amount of carbon deposit. The conversion measured along with the time on stream on these zeolite catalysts was simulated by a mechanism based on the simplified reaction path of n-octane cracking and the deactivation related to the pore blockage by carbon deposit.