• Journal of the Korean Chemical Society
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• v.25 no.2
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• pp.92-96
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• 1981

The reactions of adsorbed oxygen species, $O_2^-$ and $O^-$, with propylene on ZnO were studied by EPR spectroscopy and temperature programmed desorption technique. Propylene interacts with adsorbed $O_2^-$ at $25^{\circ}C$ and the surface intermediate was decomposed to CO, $H_2$, $CO_2$ and $CH_4$ by raising the temperature above $200^{\circ}C$, while $O^-$ gave the products of complete oxidation, $CO_2$ and $H_2O$ above $300^{\circ}C$.

• Journal of the Korean Chemical Society
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• v.39 no.5
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• pp.364-370
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• 1995

The catalytic oxidations of several olefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin (M=Ga(III), In(III), Tl(III)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were $(p-CH_3O)TPP,\;(p-CH_3)TPP,\;TPP,\;(p-F)TPP,\;(p-Cl)TPP\;and\;(F_20)TPP$ (TPP=tetraphenylporphyrin), and olefins were $(p-CH_3O)-,\;(p-CH_3)-,\;(p-H)-,\;(p-F)-,\;(p-Cl)-\;and\;(p-Br)styrene$styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the ${\sigma}^+$ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(III)- and Tl(III)-porphyrins turned out to be more active catalysts than Ga(III)-porphyrin.

• Korean Chemical Engineering Research
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• v.51 no.3
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• pp.319-324
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• 2013

The partial oxidation reaction of methane was investigated to produce syngas with $Ni/CeO_2-ZrO_2$, $Ni-Ru/CeO_2-ZrO_2$ and $Ni-Pd/CeO_2-ZrO_2$ catalysts. Honeycomb metallic monolith was applied in order to obtain high catalytic activity and stability in partial oxidation reforming. The catalysts were characterized by XRD and FE-SEM. The influence of various catalysts on syngas production was studied for the feed ratio (O/C), GHSV and temperature. Among the catalysts used in the experiment, the $Ni-Pd/CeO_2-ZrO_2$ catalyst showed the highest activity. The 99% of $CH_4$ conversion was obtained at the condition of T=$900^{\circ}C$, GHSV=10,000 $h^{-1}$ and feed ratio O/C=0.55. It was confirmed that $H_2$ yield increased slightly as O/C ratio increased, while CO yield remained almost constant. Also, $CH_4$ conversion decreased as GHSV increased. It was found that the safe range of GHSV for high $CH_4$ conversion was estimated to be less than 10,000 $h^{-1}$.

• Applied Chemistry for Engineering
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• v.19 no.6
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• pp.624-628
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• 2008

Nitrous oxide ($N_2O$), known as one of the major greenhouse gases, is an important component of the earth's atmosphere, and gives rise to precursor of acid rain and photochemical smog. For the removal of $N_2O$ and other nitrogen oxides, the SCR reaction system with various reductants is widely used. This study is based on the results of experimental and theoretical examinations on the catalytic decomposition of sole nitrous oxide ($N_2O$) and selective catalytic reduction of $N_2O$ with $CH_4$ in the presence of oxygen using mixed metal oxide catalysts obtained from hydrolatcite-type precursors. When $CH_4$ is fed together with a reductant, it affects positively on the $N_2O$ decomposition activity. At an optimum ratio of $CH_4$ to $O_2$ mole ratio, the $N_2O$ conversion activity is enhanced on the SCR reaction with partial oxidation of methane.

• Transactions of the Korean hydrogen and new energy society
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• v.12 no.3
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• pp.219-229
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• 2001

Hydrogen production by a 2-step water-splitting thermochemical cycle using metal oxides (ferrites) redox pairs and $CH_4$ have been studied in this experiment. The ferrites were reacted with $CH_4$ at $700{\sim}800^{\circ}C$ to produce CO, $H_2$ and various reduced phases (reduction step); these were then reoxidized with water vapor to generate $H_2$ in water-splitting step (oxidation step) at $600{\sim}700^{\circ}C$. The reduced ferrites, Ni-FeO and Ni-Fe alloy showed respectively different reactivity for $H_2$ formation from $H_2O$. In reduction reaction at $800^{\circ}C$, carbon was deposited on surface of Ni-ferrite due to $CH_4$ decomposition. This reduced phase containing carbon, which was taken quite different feature from other phase, produced $H_2$, CO, $CO_2$ by reacting with $H_2O$ at $600^{\circ}C$. The amount of $H_2$ evolved using reduced phase containing carbon was much higher than that of other phase.

• 한국연소학회:학술대회논문집
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• 2006.10a
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• pp.266-271
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• 2006

Characteristic of partial oxidation of methane using arc-jet plasma by AC power is investigated. Arc-jet reactor used in this work is slightly modified from typical arc jet reactor so that it can make and sustain stable state of plasma. Methane conversion, selectivity of chemicals such as hydrogen and hydrocarbon materials in the product are analyzed. Parametric approach on the performance of the reactor or detail on the partial oxidation process is carried with $O_2/C$ ratio as parameter. In addition to the results, SED and arc length is changed to understand the effect of current-voltage correlation on the reforming performance and relative role of thermal process.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.13 no.1
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• pp.462-469
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• 2012

Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.122-122
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• 1999

Graphite with its advantages of high thermal conductivity, low thermal expansion coefficient, and low elasticity, has been widely used as a structural material for high temperature. However, graphite can easily react with oxygen at even low temperature as 40$0^{\circ}C$, resulting in CO2 formation. In order to apply the graphite to high temperature structural material, therefore, it is necessary to improve its oxidation resistive property. Silicon Carbide (SiC) is a semiconductor material for high-temperature, radiation-resistant, and high power/high frequency electronic devices due to its excellent properties. Conventional chemical vapor deposited SiC films has also been widely used as a coating materials for structural applications because of its outstanding properties such as high thermal conductivity, high microhardness, good chemical resistant for oxidation. Therefore, SiC with similar thermal expansion coefficient as graphite is recently considered to be a g행 candidate material for protective coating operating at high temperature, corrosive, and high-wear environments. Due to large lattice mismatch (~50%), however, it was very difficult to grow thick SiC layer on graphite surface. In theis study, we have deposited thick SiC thin films on graphite substrates at temperature range of 700-85$0^{\circ}C$ using single molecular precursors by both thermal MOCVD and PEMOCVD methods for oxidation protection wear and tribological coating . Two organosilicon compounds such as diethylmethylsilane (EDMS), (Et)2SiH(CH3), and hexamethyldisilane (HMDS),(CH3)Si-Si(CH3)3, were utilized as single source precursors, and hydrogen and Ar were used as a bubbler and carrier gas. Polycrystalline cubic SiC protective layers in [110] direction were successfully grown on graphite substrates at temperature as low as 80$0^{\circ}C$ from HMDS by PEMOCVD. In the case of thermal MOCVD, on the other hand, only amorphous SiC layers were obtained with either HMDS or DMS at 85$0^{\circ}C$. We compared the difference of crystal quality and physical properties of the PEMOCVD was highly effective process in improving the characteristics of the a SiC protective layers grown by thermal MOCVD and PEMOCVD method and confirmed that PEMOCVD was highly effective process in improving the characteristics of the SiC layer properties compared to those grown by thermal MOCVD. The as-grown samples were characterized in situ with OES and RGA and ex situ with XRD, XPS, and SEM. The mechanical and oxidation-resistant properties have been checked. The optimum SiC film was obtained at 85$0^{\circ}C$ and RF power of 200W. The maximum deposition rate and microhardness are 2$mu extrm{m}$/h and 4,336kg/mm2 Hv, respectively. The hardness was strongly influenced with the stoichiometry of SiC protective layers.

• Journal of the Korean Applied Science and Technology
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• v.31 no.3
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• pp.446-452
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• 2014

Methanol was directly produced by the partial oxidation of methane with four-component mixed oxide catalysts. Four-component(Mo-Bi-Cr-Si) mixed oxide catalysts were prepared by the co-precipitation and sol-gel methods. The catalyst prepared by the sol-gel method showed about eleven times higher surface area than that prepared by the co-precipitation method. From the $O_2$-TPD experiment of the prepared catalysts, it was proven that there exists two types of oxygen species, and the oxygen species that participates in the partial oxidation reaction is the lattice oxygen desorbing around $750^{\circ}C$. The optimum reaction condition for methanol production was $420^{\circ}C$, 50 bar, flow rate of 115 mL/min, and $CH_4/O_2$ ratio of 10/1.5, providing methane conversion and methanol selectivity of 3.2 and 26.7%, respectively.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.580-587
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• 1994

The oxidative coupling of methane was studied kinetically using $Na^+(50wt%)/MgO$ catalyst at 710, 730, 750, 770 and $790^{\circ}C$ in a fixed bed flow reactor at the atmospheric pressure under differential conversion conditions. Through curve fitting, it was found that the Langmuir-Hinshelwood type mechanism was fitted to this reaction rather than Rideal-Redox type or Eley-Rideal type mechanism. Therefore, it was proposed that the $O_2{^-}$ or $O_2{^{2-}}$ species on the surface was related to the production of $CH_3{\cdot}$. The estimated activation energy of $CH_3{\cdot}$ production was about 39.3kcal/mol. Moreover, as the result of curve fitting, the stoichiometric coefficient of $O_2$ for the production of $CH_3{\cdot}$ to produce $CO_x$was approximately 1.5. Accordingly, it could be concluded that the $CH_3O_2{\cdot}*$ was prouduced through the partial oxidation of $CH_3{\cdot}$ with the surface oxygen.