• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.140.2-140.2
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• 2013

Strong metal-support interaction effect is an important issue in determining the catalytic activity for heterogeneous catalysis. In this work, we report the catalytic activity of $Au/TiO_2$, $Au/Al_2O_3$, and $Au/Al_2O_3-CeO_2$ nanocatalysts under CO oxidation fabricated by arc plasma deposition (APD), which is a facile dry process with no organic materials involved. These catalytic materials were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and $N_2$-physisorption. Catalytic activity of the materials has measured by CO oxidation using oxygen, as a model reaction, in a micro-flow reactor at atmospheric pressure. Using APD, the catalyst nanoparticles were well dispersed on metal oxide powder with an average particle size (3~10 nm). As for catalytic reactivity, the result shows $Au/Al_2O_3-CeO_2$ nanocatalyst has the highest catalytic activity among three samples in CO oxidation, and $Au/TiO_2$, and $Au/Al_2O_3$ in sequence. We discuss the effects of structure and metal-oxide interactions of the catalysts on catalytic activity.

• Applied Microscopy
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• v.52
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• pp.7.1-7.6
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• 2022

The process of encapsulating cobalt nanoparticles using a graphene layer is mainly direct pyrolysis. The encapsulation structure of hybrids prepared in this way improves the catalyst stability, which greatly reduces the leaching of non-metals and prevents metal nanoparticles from growing beyond a certain size. In this study, cobalt particles surrounded by graphene layers were formed by increasing the temperature in a transmission electron microscope, and they were analyzed using scanning transmission electron microscopy (STEM). Synthesized cobalt hydroxide nanosheets were used to obtain cobalt particles using an in-situ heating holder inside a TEM column. The cobalt nanoparticles are surrounded by layers of graphene, and the number of layers increases as the temperature increases. The interlayer spacing of the graphene layers was also investigated using atomic imaging. The success achieved in the encapsulation of metallic nanoparticles in graphene layers paves the way for the design of highly active and reusable heterogeneous catalysts for more challenging molecules.

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.206-214
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• 2005

Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

• Clean Technology
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• v.18 no.1
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• pp.102-110
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• 2012

In this study, the production of bio-diesel from animal oil by esterification and trans-esterification was investigated. There were three different extraction methods for oil extraction from raw animal fat. Heterogeneous catalysts such as Amberlyst-15 and Amberlyst BD-20 and a homogeneous catalyst such as sulfuric acid were used for esterification. Among three catalysts, the removal efficiency of Free Fatty Acid (FFA) was the highest in sulfuric acid. Response surface method was carried out to find the optimal esterification condition of sulfuric acid and methanol. After the esterification under the optimal condition, this animal fat was used for the trans-esterification. Animal oil used for trans-esterification was below 1% of FFA content and 0.09% of water content. The catalysts for trans-esterification were KOH, NaOH and $NaOCH_3$. To investigate the effects of catalyst type and amount on trans-esterification, The amount of catalyst were changed with 0.3, 0.6 and 0.9 wt%. The molar ratio of methanol/oil was changed with 4, 6, 9 and 12. The amount of catalyst was fixed to 0.8 wt%. The KOH catalyst showed the highest FAME conversion for trans- esterification, and the optimal methanol/oil weight ratio was 6. In the experiments of various catalysts and methanol molar ratios, the highest content of FAME is 96%. However, this FAME content was below Korean bio-diesel standard which is 96.5% of FAME content. After distillation, FAME content increased to 98%.

• Korean Chemical Engineering Research
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• v.43 no.6
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• pp.647-661
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• 2005

The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this review, we investigate the research and development trend in the asymmetric ring opening reactions using cobalt salen catalysts. Hydrolytic kinetic resolution (HKR) technology is the very prominent way to prepare optically pure terminal epoxides among available methods. We have synthesized homogeneous and heterogeneous chiral dinuclear salen complexes and demonstrated their catalytic activity and selectivity for the asymmetric ring opening of terminal epoxides with variety of nucleophiles and for asymmetric cyclization to prepare optically pure terminal epoxides in one step. The resolved ring opened product combined with ring closing in the presence of base and catalyst afforded the enantioriched terminal epoxides in quantitaive yield. Potentially, these catalysts are using on an industrial scale to produce chiral intermediates. The experimental results of HKR technology applied to the synthesis of various chiral compounds are presented in this paper.

• Applied Chemistry for Engineering
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• v.29 no.1
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• pp.62-66
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• 2018

Styrenated phenol alkoxylates (SP-A) were prepared from styrenated phenol (SP) and ethylene oxide (EO) under a homogeneous base catalyst. However, to use EO that is difficult to handle, a high-pressure reaction device capable of controlling the reaction process should be used. Additionally, when a homogeneous base catalyst is used, a neutralization process is required to remove residual bases after the reaction, and it is also difficult to separate the catalyst and the product. Therefore, in this study, we report the results of SP-A prepared from the reaction of SP and EC using only heterogeneous base catalysts. The heterogeneous base catalyst was obtained by supporting KOH on $La_2O_3$ and calcintion. Using EC instead of EO, it was possible to produce SP-A under the atmospheric rather than high-pressure reaction condition. Average molecular weights of synthesized SP-A varied greatly depending on reaction conditions. The average molecular weight of SP-A prepared using the $KOH/La_2O_3$ catalyst could be controlled arbitrarily by controlling the reaction temperature and added catalyst and EC amounts.

• Korean Chemical Engineering Research
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• v.56 no.1
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• pp.119-124
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• 2018

The production of methyl N-phenyl carbamate by an oxidative carbonylation method of aniline and methanol is of great interest as an environmentally friendly process that can replace the monomer production process of a polymer produce using conventional phosgene. In this study, heterogeneous catalysts were prepared by using Y-zeolite, $SiO_2$, $Al_2O_3$ as support, and oxidative carbonylation continuous operation from aniline and methanol was attempted using the prepared heterogeneous catalyst. Batch reactor was used to determine the support, and various reaction conditions such as reaction temperature, reaction pressure, and effect of promoter were established using palladium catalyst. A reaction kinetics study was conducted under optimum reaction conditions. The basic data for carbamate process development were obtained by performing continuous operation for a long time under established reaction condition.

• Clean Technology
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• v.24 no.4
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• pp.293-300
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• 2018

Sulfamethoxazole (SMX) is sulfaamide-based synthetic antibiotics, which are widely prescribed pharmaceutical compound to treat bacterial infections in both human and animals. Most of them are not completely decomposed as refractory substances. The environmental impact of pharmaceuticals as emerging contaminants has generated severe concerns. In this study, catalytic wet peroxide oxidation (CWPO) of SMX was carried out with $Cu/Al_2O_3$ catalyst and investigated the optimum reaction conditions of temperature, dosage of catalyst and concentration of $H_2O_2$ to completely decompose the SMX. It was observed that SMX was completely decomposed within 20 min using 0.79 mM $H_2O_2$ and 6 g $Cu/Al_2O_3$ catalyst at 1 atm and $40^{\circ}C$, but SMX was not fully mineralized and converted to intermediates as hydroylated-SMX, sulfanilic acid, 4-aminobenzenesulfinic acid and nitrobenzene. After that these are completely mineralized through organic acid. We proposed the decomposition reaction path ways of SMX by analyzing the behavior of these intermediates. To investigate the durability of heterogeneous catalyst, decomposition of SMX was observed by continuously recycling catalysts. When the heterogeneous catalyst of 10 wt% $Cu/Al_2O_3$ was continuously reused 5 times, decomposition of SMX was a little lowered, but the activity of catalyst was overall very stable.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.1-5
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• 2010

Cu(II)-organic complexes were synthesized with Lewis base organic ligands including diamine, aminothiol, and dithiol to determine the reactivity for DFP hydrolysis. Results show that the aminothiol catalyst enhances the hydrolysis of DFP in three folds compared to diamine type because aminothiol has higher basicity than diamine. Due to low solubility of Cu(II)(1,2-ethane dithiol)$(NO_3)_2$, it is impossible to compare directly the rates in homogeneous condition. However, the rate of dithol complex is even 1.6 times faster than that of the diamine type. The reactivity of zeolite for DFP hydrolysis is also evaluated. NaY type does not promote the hydrolysis, but RuNaY shows relatively lower reactivity than those of Cu(II)-organic ligands complexes.

• 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 $Al-O_2-K$.