• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.138.2-138.2
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• 2013

Copper oxide is a multi-functional material being used in various research areas including catalysis, electrochemical materials, oxidizing agents etc. Among these areas, we have synthesized and utilized graphene based copper oxide nanocomposites (CuOx/Graphene) for the catalytic applications (C-N cross coupling reaction). Briefly, Cu precursors were anchored on the graphite oxide(GO) sheets being exfoliated and oxidized from graphite powder. Two different crystalline structures of Cu2O and CuO on graphene and GO were prepared by annealing them in Ar and O2 environments, respectively. The morphological and electronic structures were systemically investigated using FT-IR, XRD, XPS, XAFS, and TEM. Here, we demonstrate that the catalytic performance was found to depend on oxidative states and morphological structures of CuOx graphene nanocomposites. The relationship between the structure of copper oxides and catalytic efficiency toward C-N cross coupling reaction will be discussed.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.147-156
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• 1992

Supported lead oxide catalysts were prepared by using ${\alpha}-,{\beta}-{\gamma}$-alumina, and MgO as a support. Among the supported lead oxide catalysts, MgO-supported catalyst showed the highest $C_2^+$ hydrocarbon selectivity for the methane conversion into $C_2^+$ hydrocarbons, but ${\gamma}$-alumina-supported PbO catalyst gave the highest $CO_2$ selectivity. And ${\alpha}$-alumina-supported catlyst showed the midium activity, whereas ${\beta}$-alumina-supported catalyst gave little activity. These reaction characteristics seemed to be largely dependent on the acticity of lattice oxygens in supported catalysts, which would be influnto be largely dependent on the activity of lattice oxygens in supported catalysts, which would be influenced in the interaction between the supports and lead oxides and the properties of supports. Especially, much higher ration of (002)/(111) peak intensities for PbO phase on MgO support than on the other supports in X-ray diffraction analysis was considered to be ab evidence that methane oxidative coupling of methane might be so-called structure-sensitive reaction, and this seemed to be an example of surface oxide-support interaction (SOSI) in the oxidative coupling reaction.

• Applied Biological Chemistry
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• v.42 no.4
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• pp.330-335
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• 1999

Pentachlorophenol(PCP), which is very persistent in soil and water environment, was tried to detoxify with oxidoreductive catalysts(peroxidase, laccase, tyrosinase and birnessite). To find out detoxification of PCP, the transformation of PCP through oxidative coupling was investigated in the presence of various oxidoreductive catalysts. PCP incubated with peroxidase was significantly transformed, however, in case of tyrosinase, the transformation was negligible. Using peroxidase, the optimal reaction condition was pH 5.6 and $16^{\circ}C$. The transformation of PCP was very fast in initiation step until 30 min but, that was not observed after 180 min. The transformation of PCP was increased by increasing peroacidase amount. When the effect of humic monomer was investigated as co-substrate on the transformation of PCP, the transformation of PCP was mostly decreased in the incubation with peroxidase, laccase, and birnessite. The transformation of PCP, however, was slightly increased by the incubation with tyrosinase in the presence of humic monomers as co-substrate, except catechol. On the basis of the results obtained, it may be suggested that PCP is able to be effectively detoxified through oxidative coupling mediated with oxidoreductive catalysts.

• Korean Journal of Environmental Agriculture
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• v.17 no.3
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• pp.239-245
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• 1998

To investigate the formation of bound residue with soil organic materials by oxidative coupling, nitroaromatics and their reduced metabolites, the insecticide parathion and the herbicide asulam were incubated with oxidoreductase, laccase or horseradish peroxidase, in the presence or absence of humic monomers. Most of aminotoluenes and amino-nitrophenols were completely transformed while most of nitrotoluenes and nitrophenols remained unchanged by a lactase or horseradish peroxidase in the presence or absence of humic monomers. Amino-nitrotoluenes were not transformed without humic monomers, but the addition of various humic monomers caused a considerable difference in the transformation of amino-nitrotoluenes by a lactase or horseradish peroxidase. Amino-nitrotoluenes were most transformed in the presence of catechol, syringaldehyde and protocatechuic acid. The insecticide parathion with nitro group and its metabolite were not mostly transformed in the presence or absence of humic monomers. The herbicide asulam with amino group remained unchanged without humic monomers as well, but the stimulating effect on the transformation of asulam was caused by the addition of catechol, syringaldehyde, protocatechuic acid or caffeic acid with a lactase.

• 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.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.807-813
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• 1993

Oxidative coupling of methane(OCM), one of the methods of direct methane conversion, was performed. Metal oxide catalysts used were Li/MgO and Pb/MgO. To investigate the reactivity of the catalysts with temperature, the reaction was carried out at 600, 700 and $800^{\circ}C$; and to investigate the effect of the feed ratio of the reactants($CH_4:O_2$) on reactivity, conversion, and selectivity the reaction was performed at $700^{\circ}C$ with the feed ratio of 2:1 and 1:1. The results indicate that 7wt% Li/MgO catalyst is a good catalyst for OCM reaction with 20% conversion and 65% selectivity at $700^{\circ}C$ with the feed ratio of 2:1. As feed ratio was 1:1, methane conversion was increased to 30% while $C_2$ selectivity decreased to 45% at $700^{\circ}C$ with 7wt% Li/MgO catalyst. The Pb/MgO catalyst showed less selectivity(25%) than Li/MgO did.

• Journal of Soil and Groundwater Environment
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• v.10 no.4
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• pp.62-69
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• 2005

Removal of 4-chlorophenol (4CP) by natural manganese dioxide (NMD) catalyzed reaction was investigated in this study. Tests were also carried out to evaluate the effects of pH and natural organic matter (NOM) on the degradative oxidation of 4CP. Experimental results proved that NMD was effective for the removal of 4CP. Extensive kinetic analysis suggests that overall oxidation of 4CP by NMD is second-order reaction, the first-order with respect to 4CP, and the first-order with respect to NMD, respectively. Also, 4CP oxidation rates on the Mn-oxide surfaces were highly dependent upon experimental conditions such as pH, initial concentration of 4CP or NMD, and existence of humic acid. As pH increased above PZC of NMD, the reaction rate of 4CP was decreased, due to the low affinity of 4CP on NMD at high pH. At pH lower than PZC of NMD, reaction rate of 4CP was also decreased. It was considered that humic acid was involved in the oxidative coupling reaction of 4CP by NMD, resulting in the enhanced degradation rate of 4CP. This study proved that natural manganese oxide can be effectively applied for the removal of chlorophenols in aqueous phase.

• Journal of Soil and Groundwater Environment
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• v.10 no.5
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• pp.45-51
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• 2005

The sorption/desorption characteristics of phenanthrene on the natural manganese oxide (NMD) were investigated in the presence of phenolic compounds. 4-chlorophenol (4-CP) was effectively oxidized by NMD catalyzed reaction and transformed into humic-like macromolecular compound through inter-or cross-coupling reaction between byproducts. As 4-CP was degraded with time, sorbed amount of phenanthrene on NMD was significantly increased, resulting from the formation of oxidative coupling products. These results imply that NMD can be used for simultaneous treatment of phenolic contaminants and polycyclic aromatic hydrocarbons (PAHs) in soils, sediments, or water. Also, sorbed phenanthrene on NMD in the presence of 4-CP showed high degree of desorption resistance, indicating that sequestration process of phenanthrene was ongoing with time.

• Journal of the Korean Applied Science and Technology
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• v.13 no.1
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• pp.67-74
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• 1996

This study was conducted to find a catalyst system which has high conversion and selectivity for the oxidative coupling of methane to produce ethane and ethylene. Various catalysts were tested in a fixed bed reactor ar $750^{\circ}C$, 1 atm, and the feed ratio($CH_4/O_2$) of 2/1. Under the reaction condition, 10wt%$PbSO_4/MgO$ catalyst showed the highest catalytic activity : methane conversion, $C_2$ selectivity and yield were 50, 40 and 20%, respectively. Catalysts containing sulfate compounds, 10wt%$PbSO_4/MgO$, 10wt%$MgSO_4/MgO$ and $Na_2SO_4/MgO$ revealed a moderate methane conversions such as 38, 50 and 50%, respectively and low $C_2$ selectivities such as 18, 5 and 9%, respectively. Catalysts containing carbonate compounds, 10wt%$PbCO_3/MgO$, 10wt%$Li_2CO_3/MgO$ and $NaCO_3/MgO$, also showed a moderate methane conversions such as 64, 44 and 51%, respectively and low $C_2$ selectivities such as 5, 6 and 2%, respectively. With the existence of chlorine and mercury, $C_2$ selectivity was decreased.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.1979-1984
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• 2014

We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in $H_2$ and $O_2$ gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.