• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2099-2104
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• 2013

We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

• Clean Technology
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• v.21 no.2
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• pp.130-139
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• 2015

The NO oxidation process has been applied to improve a removal efficiency of NO included in exhaust gas. In this study, to produce a dry oxidant for the NO oxidation process, the catalytic H₂O₂ decomposition method was proposed. A variety of the heterogeneous solid-acidic Mn-based catalysts were prepared for the catalytic H₂O₂ decomposition and the effect of their physico-chemical properties on the catalytic H₂O₂ decomposition were investigated. The results of this study showed that the acidic sites of the Mn-based catalysts has an influence on the catalytic H₂O₂ decomposition. The Mn-based catalyst having the abundant acidic sites within the wide temperature range in NH₃-TPD shows the best performance for the catalytic H₂O₂ decomposition. Therefore, the NO oxidation efficiency, using the dry oxidant produced by the H₂O₂ decomposition over the Mn-based catalyst having the abundant acidic properties under the wide temperature range, was higher than the others. As a remarkable result, the best performances in the catalytic H₂O₂ decomposition and NO oxidation was shown when the Mn-based Fe₂O₃ support catalyst containing K component was used for the catalytic H₂O₂ decomposition.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.245-245
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• 2012

Syntheses of oxide supported metal catalysts by wet-chemical routes have been well known for their use in heterogeneous catalysis. However, uniform deposition of metal nanoparticles with controlled size and shape on the support with high reproducibility is still a challenge for catalyst preparation. Among various synthesis methods, arc plasma deposition (APD) of metal nanoparticles or thin films on oxide supports has received great interest recently, due to its high reproducibility and large-scale production, and used for their application in catalysis. In this work, Au and Pt nanoparticles with size of 1-2 nm have been deposited on titania powder by APD. The size of metal nanoparticles was controlled by number of shots of metal deposition and APD conditions. These catalytic materials were characterized by x-ray diffraction (XRD), inductively coupled plasma (ICP-AES), CO-chemisorption and transmission electron microscopy (TEM). Catalytic activity of the materials was measured by CO oxidation using oxygen, as a model reaction, in a micro-flow reactor at atmospheric pressure. We found that Au/$TiO_2$ is reactive, showing 100% conversion at $110^{\circ}C$, while Pt/$TiO_2$ shows 100% conversion at $200^{\circ}C$. High activity of metal nanoparticles suggests that APD can be used for large scale synthesis of active nanocatalysts. We will discuss the effect of the structure and metal-oxide interactions of the catalysts on catalytic activity.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.415-418
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• 2010

Highly ordered mesoporous silver material was successfully synthesized from a mesoporous silica template (KIT-6) with 3-D channel structure using the nano-replication method. The effects of $H_2$ or $O_2$ pretreatments on the catalytic performance of the mesoporous silver were investigated using a temperature programmed CO oxidation technique in a fixed bed reactor. The mesoporous silver material that was pretreated with $H_2$ exhibited an excellent catalytic activity compared to the as-prepared and $O_2$-pretreated catalysts. Moreover, this present mesoporous silver material showed good catalytic stability. For the CO oxidation, the apparent activation energy of the $H_2$-pretreated mesoporous silver catalyst was $61{\pm}0.5\;kJ\;mol^{-1}$, which was also much lower than the as-prepared ($132{\pm}1.5\;kJ\;mol^{-1}$) and $O_2$-pretreated ($124{\pm}1.4\;kJ\;mol^{-1}$) catalysts.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.343-348
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• 2016

Manganese and $TiO_2$ grown on Activated Carbon Fiber (ACF) was synthesized by hydrothermal method. The prepared composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX). The catalytic behavior was investigated through the decomposition of methylene blue (MB) and methyl orange (MO) as standard dyes under visible light. The degradation performance of the degraded standard dye solutions was determined by UV-Vis spectrophotometry. This enhanced photocatalytic activity arises from the positive synergetic effect among the Mn, $TiO_2$ and ACF in this heterogeneous photocatalyst. The process contributes to the release of abundant photocatalytic sites of Mn and $TiO_2$ and improves the photocatalytic efficiency. The excellent adsorption and photocatalytic effect with the explanation of the synergetic mechanism are very useful not only for fundamental research but also for potential practical applications.

• Korean Chemical Engineering Research
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• v.54 no.1
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• pp.64-69
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• 2016

The applications of heterogeneous catalyst have been relatively active area of research in the biodiesel process. These catalysts have the benefit of easy recovery and reusability of the catalyst. The objective of this study is to find out significant effect of calcination temperature on $K_2CO_3/{\gamma}-Al_2O_3$ catalytic activity in the biodiesel formation reaction. As a results, the temperature at which a catalyst was calcined had very important influence on the catalytic activity. The catalytic activity increased up to $600^{\circ}C$, but it severely decreased above the temperature. The reduction of catalyst activity at high temperature would be due to the deduction of the active sites of Al-O-K and $Al-O_2-K$.

• Transactions of the Korean Society of Automotive Engineers
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• v.20 no.6
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• pp.73-82
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• 2012

The main and side reactions of the three selective catalytic reduction (SCR) reactions with ammonia over a vanadium-based catalyst have been investigated using synthetic gas mixtures in the temperature range of $170{\sim}590^{\circ}C$. The three SCR reactions are standard SCR with pure NO, fast SCR with an equimolar mixture of NO and $NO_2$, and $NO_2$ SCR with pure $NO_2$. Vanadium based catalyst has no significant activity in NO oxidation to $NO_2$, while it has high activity for $NO_2$ decomposition at high temperatures. The selective catalytic oxidation of ammonia and the formation of nitrous oxide compete with the SCR reactions at the high temperatures. Water strongly inhibits the selective catalytic oxidation of ammonia and the formation of nitrous oxide, thus increasing the selectivity of the SCR reactions. However, the presence of water inhibits the SCR activity, most pronounced at low temperatures. In this study, the experimental results are analyzed by means of a dynamic one-dimensional isothermal heterogeneous plug-flow reactor (PFR) model according to the Eley-Rideal mechanism.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.130-131
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• 2013

Nanostructured oxides are widely used in heterogeneous catalysis where their catalytic properties are closely associated with the size and morphology at nanometer level. The effect of particle size has been well decumented in the past two decades, but the shape of the nanoparticles has rarely been concerned. Here we illustrate that the redox and acidic-basic properties of oxides are largely dependent on their shapes by taking $Co_3O_4$, $Fe_2O_3$, $CeO_2$ and $La_2O_3$ nanorods as typical examples. The catalytic activities of these rod-shaped oxides are mainly governed by the nature of the exposed crystal planes. For instance, the predominant presence of {110} planes which are rich in active $Co^{3+}$ on $Co_3O_4$ nanorods led to a much higher activity for CO oxidation than the nanoparticles that mainly exposed the {111} planes. The simultaneous exposure of iron and oxygen ions on the surface of $Fe_2O_3$ nanorods have significantly enhanced the adsorption and activation of NO and thereby promoted the efficiency of DeNOx process. Moreover, the exposed surface planes of these rod-shaped oxides mediated the reaction performance of the integrated metal-oxide catalysts. Au/$CeO_2$ catalysts exhibited outstanding stability under water-gas shift conditions owing to the strong bonding of gold particle on the $CeO_2$ nanorods where the formed gold-ceria interface was resistant towards sintering. Cu nanoparticles dispersed on $La_2O_3$ nanorods efficiently catalyzed transfer dehydrogenation of primary aliphatic alcohols based on the uniue role of the exposed {110} planes on the support. Morphology control at nanometer level allows preferential exposure of the catalytically active sites, providing a new stragegy for the design of highly efficient nanostructured catalysts.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.11
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• pp.1054-1062
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• 2010

Oxidative coupling reactions of humic substances (HS) can be catalyzed by a variety of natural extracellular enzymes and metal oxides. In this study, property changes of HS induced by a natural enzyme, horseradish peroxidase (HRP), and the effect of it to microfiltration (MF) were investigated. PAHA was transformed by oxidative coupling reaction with HRP and hydrogen peroxide ($H_2O_2$), verifying the catalytic effects of the HRP. Size exclusion chromatography (SEC) revealed that weight-average molecular weight (MWw) of PAHA was proportionally increased with the dosages of HRP and $H_2O_2$, indicating the transform action of HS into larger and complex molecules. An increase in the conformational stability of HS was achieved through the promotion of intermolecular covalent bondings between heterogeneous humic molecules. Spectroscopic analysis (fluorescence and infrared spectroscopy) proved that functional groups were transformed by the reaction. Additionally, HS and transformed products were undergone microfiltration (MF) to examine the treatment potential of them in a water treatment facility. Original HS could not be removed by MF but larger molecules of transformed products could be removed. Meanwhile, transformed products caused more fouling on the filtration than original HS. This results proved that natural organic matter (NOM) can be removed by MF after its increase in molecular size by oxidative coupling reaction.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.418-425
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• 2013

The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/$Al_2$ ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption ($NH_3$-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/$Al_2$ ratio of ZSM-5 is about 50~80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of $437^{\circ}C$ and WHSV of $0.8h^{-1}$.