• 제목/요약/키워드: heterogeneous chemical reaction

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Heterogeneous Catalysts Fabricated by Atomic Layer Deposition

  • Kim, Young Dok
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.128-128
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    • 2013
  • Fabrication of heterogeneous catalysts using Atomic Layer Deposition (ALD) has recently been attracting attention of surface chemists and physicists. In this talk, I will present recent results about structures and chemical activities of various catalysts prepared by ALD, particularly focusing on Ni-based catalysts. Ni has been considered as potential catalysts for $CO_2$ reforming of methane (CRM); however, Ni often undergoes rapid decrease in catalytic activity with time, and therefore, application of Ni as catalysts for CRM has been regarded as difficult so far. Deactivation of Ni catalysts during CRM reaction is from either coke formation on Ni surface or sintering of Ni particles during reaction. Two different strategies have been used for enhancing stability of Ni-based catalysts; $TiO_2$ nanoparticles were deposited on micrometer-size Ni particles by ALD, which turned out to reduce coke formation on Ni surfaces. Ni nanoparticles deposited by ALD on mesoporous silica showed high activity and long-term stability from CRM without coke deposition and sintering during CRM reaction. Ni-based catalysts have been also used for oxidation of toluene, which is one of the most notorious gases responsible for sick-building syndrome. It was shown that onset-temperature of Ni catalysts for toluene oxidation is as low as $120^{\circ}C$. At $250\circ}C$, total oxidation of toluene to $CO_2$ with a 100% conversion was found.

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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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    • v.55 no.2
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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.

Styrene Epoxidation over Cobalt Cyclam Immobilized SBA-15 Catalyst

  • Sujandi;Prasetyanto, Eko Adi;Han, Sang-Cheol;Park, Sang-Eon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1381-1385
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    • 2006
  • Cobalt (cyclam) complex has been successfully immobilized onto SBA-15, and proven to be an active catalyst for the epoxidation of styrene with tert-butyl hydroperoxide as a terminal oxidant. The selectivity for styrene oxide was observed to be up to 66% with 40% styrene conversion after 12h reaction time. The reversible redox cycle between Co(III) and Co(II) couple which was supposed to play key role during the epoxidation reaction was supported by a cyclic voltametry analysis. The textural properties of the catalyst was characterized by XRD, N2 adsorption-desorption, and TEM analysis.

Carbon-Based Solid Acid as an Efficient and Reusable Catalyst for the Synthesis of 1,8-Dioxodecahydroacridines Under Solvent-Free Conditions

  • Davoodnia, Abolghasem;Khojastehnezhad, Amir;Tavakoli-Hoseini, Niloofar
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2243-2248
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    • 2011
  • Carbon-based solid acid catalyst was found to be highly efficient, eco-friendly and recyclable heterogeneous catalyst for the multicomponent reaction of dimedone, aromatic aldehydes, and a nitrogen source (ammonium acetate or aromatic amines) under solvent-free conditions, giving rise to 1,8-dioxodecahydroacridines in high yields. The present methodology offers several advantages, such as a simple procedure with an easy work-up, short reaction times, high yields, and the absence of any volatile and hazardous organic solvents.

An Efficient and Environmentally Friendly Procedure for the Synthesis of Some Novel 8-Benzylidene-4-phenyl-3,4,5,6,7,8-hexahydro-1H-quinazolin-2-ones/thiones using Tetrabutylammonium Hexatungstate as a Reusable Heterogeneous Catalyst under Solvent-Free Conditions

  • Ghashang, Majid;Mansoor, Syed Sheik;Aswin, Krishnamoorthy
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3289-3294
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    • 2013
  • An efficient method for the preparation of 8-benzylidene-4-phenyl-3,4,5,6,7,8-hexahydro-1H-quinazolin-2-ones/thiones from the reaction of aromatic aldehydes with cyclohexanone and urea or thiourea in the presence of Tetrabutylammonium hexatungstate, $[TBA]_2[W_6O_{19}]$, as an efficient, inexpensive catalyst under thermal and solvent-free conditions has been developed. Good yields, short reaction times, straightforward workup, reusability of the catalyst, and green conditions are the most obvious advantages of this procedure.

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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    • v.9 no.2
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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.

Unsteady Mass Transfer Around Single Droplet Accompanied by Interfacial Extraction Reaction of Succinic Acid (숙신산 추출반응이 일어나는 단일 액적계에서의 비정상상태 물질 전달)

  • Jeon, Sangjun;Hong, Won Hi
    • Korean Chemical Engineering Research
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    • v.50 no.6
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    • pp.1021-1026
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    • 2012
  • The transient mass transfer in a single droplet system consisting of 1-octanol (continuous phase)/aqueous succinic acid solution (dispersed phase) was investigated in the presence of chemical reaction, which is acid/anion exchange reaction of succinic acid and tri-n-octylamine (TOA). This succinic acid extraction by TOA can be considered to occur at the interface between organic and aqueous phase, that is, heterogeneous reaction system. The basic properties of the system such as viscosity, density, distribution coefficient, terminal velocity of droplet, and diffusion coefficient were measured experimentally or calculated theoretically, and used for theoretical calculation of characteristic parameters of mass transfer later. The effects of succinic acid concentration on the terminal velocity was negligible in the existence of TOA, although the terminal velocity increases with succinic acid concentration in the absence of TOA. On the contrary, the terminal velocity decreases with TOA concentration. While droplets falls through organic phase, the trajectory of droplets is observed to oscillate around its vertical path. A mass trnasfer cell was prepared to monitor the mass transfer behavior in a single droplet and used to measure the mean concentration of succinic acid inside droplet. The results are expressed with dimensionless parameters. Under 50 g/L succinic acid condition, the system with 0.1 mol/kg TOA showed that the molar flux decreases in proportion to the decrease of concentration gradient, while in the case of 0.5 mol/kg TOA Sh increases rapidly with time indicating the molar flux of succinic acid decreases relatively slowly compared to the decrease in concentration gradient.

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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    • v.30 no.4
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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.

An Experimental and Modeling Study on the Oxidation Kinetics of Nitric Oxide over Platinum-based Catalysts (백금계 촉매상에서 산화질소(NO)의 산화반응속도에 관한 실험 및 모델링 연구)

  • Kim, Young-Deuk;Jeong, Soo-Jin;Kim, Woo-Seung
    • Transactions of the Korean Society of Automotive Engineers
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    • v.20 no.5
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    • pp.71-80
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    • 2012
  • To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

Polymer-Supported Crown Ethers(Ⅳ) Synthesis and Phase-transfer Catalytic Activity

  • Shim Jae Hu;Chung Kwang Bo;Masao Tomoi
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.274-279
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    • 1992
  • Immobilization method of lariat azacrown ethers, containing hydroxyl group in the side arm of crown ring, on the polymer matrix and the phase-transfer catalytic activity of thus obtained immobilized lariat azacrown ethers were studied. Polystyrene resins with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of crosslinked polystyrene resins containing epoxy groups with monoaza-15-crown-5 or monoaza-18-crown-6. Microporous crosslinked polystyrene resins containing epoxy group for the syntheses of these immobilized lariat crown catalysts were prepared by suspension polymerization of styrene, divinylbenzene (DVB 2%) and vinylbenzylglycidyl ether. The immobilized lariat catalysts with 10-20% ring substitution exhibited maximal activity for the halogen exchange reactions of 1-bromooctane with aqueous KI or NaI under triphase heterogeneous conditions. Immobilized catalyst exhibited higher activity than corresponding catalyst without the hydroxyl group and this result was suggested that the active site have a structure in which the $K^+$ ion was bound by the cooperative coordination of the crown ring donors and the hydroxyl group in the side arm.