• Title/Summary/Keyword: Heterogeneous Surface Reaction

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P123-Templated Co3O4/Al2O3 Mesoporous Mixed Oxides for Epoxidation of Styrene

  • Jung, Mie-Won;Kim, Young-Sil
    • 한국재료학회지
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    • 제22권6호
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    • pp.316-320
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    • 2012
  • $Co_3O_4$, $Al_2O_3$ and $Co_3O_4$/$Al_2O_3$ mesoporous powders were prepared by a sol-gel method with starting matierals of aluminum isopropoxide and cobalt (II) nitrate. A P123 template is employed as an active organic additive for improving the specific surface area of the mixed oxide by forming surfactant micelles. A transition metal cobalt oxide supported on alumina with and without P123 was tested to find the most active and selective conditions as a heterogeneous catalyst in the reaction of styrene epoxidation. A bBlock copolymer-P123 template was added to the staring materials to control physical and chemical properties. The properties of $Co_3O_4$/$Al_2O_3$ powder with and without P123 were characterized using an X-ray diffractometer (XRD), a Field-Emission Scanning Electron Microscope (FE-SEM), a Bruner-Emmertt-Teller (BET) surface analyzer, and $^{27}Al$ MAS NMR spectroscopy. Powders with and without P123 were compared in catalytic tests. The catalytic activity and selectivity were monitored by GC/MS, $^1H$, and $^{13}C$-NMR spectroscopy. The performance for the reaction of epoxidation of styrene was observed to be in the following order: [$Co_3O_4$/$Al_2O_3$ with P123-1173 K > $Co_3O_4$/$Al_2O_3$ with P123-973 K > $Co_3O_4$-973 K>$Co_3O_4$/$Al_2O_3$-973 K > $Co_3O_4$/$Al_2O_3$ with P123-1473 K > $Al_2O_3$-973 K]. The existence of ${\gamma}$-alumina and the nature of the surface morphology are related to catalytic activity.

The Oxidation of Functionally Gradient NiCrAlY/YSZ Coatings

  • Park, K.B.;Park, H.S.;Kim, H.J.;Lee, D.B.
    • 한국표면공학회지
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    • 제34권5호
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    • pp.499-502
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    • 2001
  • Functionally gradient NiCrAlY/$ZrO_2$-$Y_2$$O_3$ and NiCrAlY/$ZrO_2$- $CeO_2$-$Y_2$$O_3$ coatings were prepared by APS. The as-sprayed microstructure consisted of metal-rich and ceramic-rich regions, between which $Al_2$$O_3$-rich layers existed owing to the oxidation during APS. During oxidation between 900 and $1100^{\circ}C$ in air, the pre-existing $Al_2$$O_3$-rich scales grew, due mainly to the preferential reaction of Al with inwardly transporting oxygen along the heterogeneous phase boundaries. As the amount of ceramics in the coating increased, the oxidation resistance increased.

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시동 특성, 수소 생산 및 선택성 향상을 위한 자열개질기의 이론 및 수치해석적 연구 (Theoretical and numerical study to investigate characteristics of light-off and steady state of methane autothermal reactor for efficient light-off, high hydrogen yield and selectivity)

  • 이신구;배중면
    • 대한기계학회:학술대회논문집
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    • 대한기계학회 2007년도 춘계학술대회B
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    • pp.3353-3358
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    • 2007
  • The present paper is devoted to investigate dynamic effect and steady-state performance of methane autothermal reformer theoretically and numerically. In order to simplify the complicated phenomena in the system, axisymmetric heterogeneous reactor model is developed. As autothermal reaction takes places on catalyst surface between bulk gas and catalyst, volume averaging method is incorporated using porous medium approach. To understand the start-up process which occurs in the reactor is highly important. Therefore, in this paper we get various goverining equations to find out transient and steady solutions and time scale for start-up introducing dimensionless variables. Start-up is a significant issue in reforming reaction for automobile system and fueling of SOFC-based auxiliary power units. This paper deals with characteristics of heat and mass transfer and predicted light-off time in the reformer as oxygen to carbon ratio ($O_2$/C) and amount of feeding gas.

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High Selective Oxidation of Alcohols Based on Trivalent Ion (Cr3+ and Co3+) Complexes Anchored on MCM-41 as Heterogeneous Catalysts

  • Shojaei, Abdollah Fallah;Rafie, Mahboubeh Delavar;Loghmani, Mohammad Hassan
    • Bulletin of the Korean Chemical Society
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    • 제33권8호
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    • pp.2748-2752
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    • 2012
  • Cr(III) and Co(III) complexes with acetylacetonate were anchored onto a mesoporous MCM-41 through Schiff condensation. The materials were characterized by XRD, FT-IR, BET, CHN and ICP techniques. Elemental analysis of samples revealed that one C=N bond was formed through Schiff condensation on MCM-41 surface. The catalysts were tested for the alcohol oxidations using t-butyl hydroperoxide (TBHP) and $H_2O_2$ as oxidant. The catalytic experiments were carried out at both room temperature and reflux condition. Various solvents such as dichloromethane, acetonitrile and water were examined in the oxidation of alcohols. Among the different solvents, catalytic activity is found more in acetonitrile. Further, the catalysts were recycled three times in the oxidation of alcohols and no major change in the conversion and selectivity is observed, which shows that the immobilized metal-acetylacetonate complexes are stable under the present reaction conditions.

Degradation of Phenol with Fenton-like Treatment by Using Heterogeneous Catalyst (Modified Iron Oxide) and Hydrogen Peroxide

  • Lee, Si-hoon;Oh, Joo-yub;Park, Yoon-chang
    • Bulletin of the Korean Chemical Society
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    • 제27권4호
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    • pp.489-494
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    • 2006
  • Goethite, hematite, magnetite and synthesized iron oxide are used as catalysts for Fenton-type oxidation of phenol. The synthesized iron oxides were characterized by X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The catalytic activity of these materials is classified according to the observed rate of phenol oxidation. The effectiveness of the catalysts followed the sequence: ferrous ion > synthesized iron oxide >> magnetite hematite > goethite. According to these results, the most effective iron oxide catalyst had the structure similar to natural hematite. The surface oxidation state of the catalyst was between magnetite and hematite (+2.5 ~ +3.0). Phenol degraded completely in 40 min at neutral pH (pH = 7). Soluble ferric and ferrous ions were not detected in the filtrate from Fenton reaction solution by AAS. The formation of hydroxyl radicals was confirmed by EPR.

Fabrication of Double-Doped Magnetic Silica Nanospheres and Deposition of Thin Gold Layer

  • Park, Sang-Eun;Lee, Jea-Won;Haam, Seung-Joo;Lee, Sang-Wha
    • Bulletin of the Korean Chemical Society
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    • 제30권4호
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    • pp.869-872
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    • 2009
  • Double-doped magnetic particles that incorporated magnetites into both the surface and inside the silica cores were fabricated via the sol-gel reaction of citrate-stabilized magnetites with silicon alkoxide. Double-doped magnetic particles were easily fabricated and exhibited an higher magnetism in comparison to the singledoped magnetic particles that were prepared by the erosion of surface-deposited magneties from double-doped magentic particles. Thin gold layer was formed over magnetic silica nanospheres via nanoseed-mediated growth of gold clusters. The plasmon-derived absorption bands of double-doped magnetic silica-gold nanoshells were more broadened and shifted down by ca. 20 nm as compared to those of single-doped magnetic silicagold nanoshells, which were attributed to not only the surface scattering of incident light due to relatively rough surafce morphology, but also heterogeneous permittivity of dielectric cores due to surface-deposited magnetites.

Kinetics and Mechanism of the Oxidation of Carbon Monoxide on H$_2$-Reduced NiO-Doped $\alpha$-Fe$_2O_3$

  • Kim, Don;Kim, Keu-Hong;Choi, Jae-Shi
    • Bulletin of the Korean Chemical Society
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    • 제9권2호
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    • pp.81-84
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    • 1988
  • The CO oxidation was performed on $H_2$-reduced NiO-${\alpha}-Fe_2O_3$ in the temperature range 150-$250^{\circ}C$. The kinetic study and the conductivity measurements indicate the oxidation reaction follows Langmuir-Rideal type process that is uncommon in heterogeneous catalyst$^1$. No active site is found on the catalyst surface for CO adsorption, but an oxygen vacancy adsorbs an oxygen, and this step is rate initiation. The partial orders are half for $O_2$ and first for CO, respectively. Apparent activation energy for over-all reaction is 9.05 kcal/mol.

Studies of the Organic Molecules Dissociative Surface Ionization in the Mass-Spectrometric Surface Ionization Method

  • Ilkhomjan Saydumarov;Dilshadbek Usmanov
    • Mass Spectrometry Letters
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    • 제15권1호
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    • pp.54-61
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    • 2024
  • An improved voltage modulation method (VMM) was used to control the heat release and adsorption properties of the adsorbent. In this work, the voltage and flux modulation methods were considered under unified experimental conditions of dissociative surface ionization (SI) of polyatomic organic molecules, the criteria were found when under VMM conditions the current relaxation of SI carries information about the kinetic properties of thermal desorption of ionizable dissociation particles arriving on the surface of polyatomic molecules. Conditions were found under which the relaxation of the ionic current in the flux modulation method is determined by the kinetics of the heterogeneous dissociation reaction of the original polyatomic molecules. The values of the thermal desorption rate constant K+ and the activation energy E+ obtained with VMM for desorption of (CH3)2NCH+2 ions with m/z 58 by adsorption of imipramine and amitriptyline molecules agree well with each other and with the results for the desorption of the same ions by adsorption of other molecules. This confirms one of the basic conditions for the equilibrium process SI - the a degree (β coefficient) of the same particles SI on the same emitter surface is the same and does not depend on the way these particles are formed on the emitter surface.

Modeling on Hydrogen Effects for Surface Segregation of Ge Atoms during Chemical Vapor Deposition of Si on Si/Ge Substrates

  • Yoo, Kee-Youn;Yoon, Hyunsik
    • Korean Chemical Engineering Research
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    • 제55권2호
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    • pp.275-278
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    • 2017
  • Heterogeneous semiconductor composites have been widely used to establish high-performance microelectronic or optoelectronic devices. During a deposition of silicon atoms on silicon/germanium compound surfaces, germanium (Ge) atoms are segregated from the substrate to the surface and are mixed in incoming a silicon layer. To suppress Ge segregation to obtain the interface sharpness between silicon layers and silicon/germanium composite layers, approaches have used silicon hydride gas species. The hydrogen atoms can play a role of inhibitors of silicon/germanium exchange. However, there are few kinetic models to explain the hydrogen effects. We propose using segregation probability which is affected by hydrogen atoms covering substrate surfaces. We derived the model to predict the segregation probability as well as the profile of Ge fraction through layers by using chemical reactions during silicon deposition.