• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.129-129
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• 2013

Nanometal alloy catalysts have been found to significantly increase catalytic efficiency, compared to the monometallic counterparts. This enhancement can be attributed to various alloying effects: i) the existence of uniquemixed-metal surface sites [the so called ensemble (geometric) effect]; ii) electronic state changes due to metal-metal interactions [the so called ligand (electronic) effect]; and iii) strain caused by lattice mismatch between the alloy components [the socalled strain effect]. In addition, the presence of low-coordination surface atoms and preferential exposure of specific facets [(111), (100), (110)] in association with the size and shape of nanoparticle catalysts [the so called shape-size-facet effect] can be another important factor for modifying the catalytic activity. However, mechanisms underlying the alloying effect still remain unclear owing to the difficulty of direct characterization. Computational approaches, particularly the prediction using first-principles density functional theory (DFT), can be a powerful and flexible alternative for unraveling the role of alloying effects in catalysis since those can give us quantitative insights into the catalytic systems. In this talk, I will present the underlying principles (such as atomic arrangement, facet, local strain, ligand interaction, and effective atomic coordination number at the surface) that govern catalytic reactions occurring on Pd-based alloys using the first-principles calculations. This work highlights the importance of knowing how to properly tailor the surface reactivity of alloy catalysts for achieving high catalytic performance.

• Macromolecular Research
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• 제14권1호
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• pp.101-106
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• 2006

The transport of reactant gas, electrons and protons at the three phase interfaces in the catalytic layers of membrane electrode assemblies (MEAs) in proton exchange, membrane fuel cells (PEMFCs) must be optimized to provide efficient transport to and from the electrochemical reactions in the solid polymer electrolyte. The aim of reducing proton transport loss in the catalytic layer by increasing the volume of the conducting medium can be achieved by filling the voids in the layer with small-sized electrolytes, such as dendrimers. Generation 1.5 and 3.5 polyamidoamine (PAMAM) dendrimer electrolytes are well-controlled, nanometer-sized materials with many peripheral ionic exchange, -COOH groups and were used for this purpose in this study. The electrochemically active surface area of the deposited catalyst material was also investigated using cyclic voltammetry, and by analyzing the Pt-H oxidation peak. The performances of the fuel cells with added PAMAM dendrimers were found to be comparable to that of a fuel cell using MEA, although the Pt utilization was reduced by the adsorption of the dendrimers to the catalytic layer.

• Bulletin of the Korean Chemical Society
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• 제25권9호
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• pp.1355-1360
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• 2004

The oxidative decomposition of trichloroethylene (TCE) was investigated using palladium catalysts supported on pure and sulfated zirconia. The reactions were performed under dry and wet conditions in the temperature between 200 and $550^{\circ}C$ keeping GHSV of 14,000 $h^{-1}.$ The products such as $C_2Cl_4,\;C_2HCl_5,\;CO\;and\;CO_2$ were observed in the reaction. The addition of water in the feed affected the distribution of reaction product with dramatically improved catalytic activity. The spectroscopic investigations gave an evidence that the strong acid sites play an important role on controlling the catalytic activity. Among the catalysts investigated, the Pd-loaded sulfated zirconia catalyst with 1 wt% Pd was found to exhibit the highest catalytic activity in the presence of water vapor having the stability for 30 h of the reaction at $500^{\circ}C$. The successful performance of the catalyst might be attributed to promotional effect of Pd active sites and strong acid sites induced from surface sulfate species on zirconia.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2009년도 제38회 동계학술대회 초록집
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• pp.35-35
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• 2010

Understanding the mechanistic details of heterogeneous catalytic reactions will provide a way to tune the selectivity between various competing reaction channels. In this regard, catalytic decomposition of alcohols over the rutile $TiO_2$(110) surface as a model oxide catalyst has been studied to understand the reaction mechanism employing the temperature-programmed desorption (TPD) technique. The $TiO_2$(110) model catalyst is found to be active toward alcohol dehydration. We find that the active sites are bridge-bonded oxygen vacancies where RO-H heterolytically dissociates and binds to the vacancy to produce alkoxy (RO-) and hydroxyl (HO-). Two protons adsorbed onto the bridge-bonded oxygen atoms (-OH) readily react with each other to form a water molecule at ~500 K and desorb from the surface. The alkoxy (RO-) undergoes decomposition at higher temperatures into the corresponding alkene. Here, the overall desorption kinetics is limited by a first-order decomposition of intermediate alkoxy (RO-) species bound to the vacancy. We show that detailed analysis on the yield and the desorption temperatures as a function of the alkyl substituents provides valuable insights into the reaction mechanism. After the catalytic role of the oxygen vacancies has been established, we employed x-ray photoelectron spectroscopy to further study the surface electronic structure related to the catalytically active defective sites. The defect-related state in valence band has been related to the chemically reduced $Ti^{3+}$ defects near the surface region and are found to be closely related to the catalytic activity of the $TiO_2$(110) surface.

• BMB Reports
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• 제41권8호
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• pp.609-614
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• 2008

The concentrations and catalytic activities of enzymes control metabolic rates. Previous studies have focused on enzyme concentrations because there are no genome-wide techniques used for the measurement of enzyme activity. We propose a method for evaluating the significance of enzyme activity by integrating metabolic network topologies and genome-wide microarray gene expression profiles. We quantified the enzymatic activity of reactions and report the 388 significant reactions in five perturbation datasets. For the 388 enzymatic reactions, we identified 70 that were significantly regulated (P-value < 0.001). Thirty-one of these reactions were part of anaerobic metabolism, 23 were part of low-pH aerobic metabolism, 8 were part of high-pH anaerobic metabolism, 3 were part of low-pH aerobic reactions, and 5 were part of high-pH anaerobic metabolism.

• 한국자동차공학회논문집
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• 제18권6호
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• pp.46-52
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• 2010

In this paper, emission analysis during cold start period of CVS-75 mode in LPG vehicle was performed to find out proper operating conditions of SAI(Secondary Air Injection) system. In order to meet SULEV target, the simulated emission system had a SAI system as well as a MCC(Manifold Catalytic Converter) and a UCC(Under body Catalytic Converter). Using commercial 1-D code AMESIM, in which 7 step global surface chemical reactions of Langmuir-Hinshelwood type were adopted, transient emission analysis in the exhaust system during cold start period of CVS-75 mode were carried out to figure out the effects of flow rate, duration of supply air on HC, CO, NO emission.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2644-2648
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• 2010

Catalytic conversion of structurally different epoxides to the corresponding 1,2-diacetoxy esters was carried out readily with phosphomolybdic acid alone or its supported on $SiO_2$. The reactions were carried out under solvolytic or solvent free conditions within 5-15 min at room temperature. The product 1,2-diacetates were obtained in high to excellent yields. Supporting of phosphomolybdic acid on $SiO_2$ showed the better catalytic activity than $Al_2O_3$. Conversion of optically pure R-(+)-styrene oxide to S-(+)-1,2-diacetoxy-1-phenylethane was carried with phosphomolybdic acid in high yield and stereospecificity.

• 대한화학회지
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• 제12권3호
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• pp.128-137
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• 1968

In the oligomerization of p-aminophenol by the catalytic action of Fe-EDTA complex in the aqueous medium, the mixed complex intermediate, Fe-EDTA-M type, is considered to be formed, from which active radicals of the monomer are produced. In this system, polymerization is presumed to proceed as follows: Free radical formation ${\to}$ Coupling ${\to}$ Activation ${\to}$ Coupling, and so on. In this study, the form of the monomer and coordination state in the mixed complex, the catalytic action of Fe-EDTA the complex, the reaction mechanism, and the structure of the oligomers are discussed.

• 대한화학회지
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• 제12권3호
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• pp.114-120
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• 1968

Fe-EDTA complex, which is easily formed when Fe salt and EDTA.2Na are mixed in the aqueous medium, is found to be a very effective catalyst in the dehydropolycondensation of aminophenols. In the dehydropolycondensation of aminophenols, the catalyst, Fe(Ⅲ)-EDTA complex (higher oxidation state) is reduced to less stable Fe(Ⅱ)-EDTA complex (lower oxidation state), and the latter is easily oxidized by air to the original higher oxidation state complex, therefore the catalytic action of Fe-EDTA complex is found to be recycled effectively. Under the catalytic action of the above mentioned complex, p-aminophenol is polymerized in the aqueous medium to form the oligomers of p-aminophenol, which the degree of polymerization to be 5 or more. The oligomers formed contain partly quinone nucleus as well as amino and hydroxyl groups. In this study, the effects of the solvents and characteristics of the oligomers are discussed. These types of polymerizations catalyzed by the metallic chelate compounds are considered to be very closely related to the reactions in the living matters.

• Bulletin of the Korean Chemical Society
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• 제27권2호
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• pp.255-265
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• 2006

The oxidation of hydrazobenzene by molecular oxygen in the polar solvent methanol is catalysed by a Schiff's base complex Co(3MeOsalen) which is a synthetic oxygen carrier. The products are trans-azobenzene and water. The rate of the reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a ternary complex of catalyst, hydrazobenzene and molecular oxygen has been proposed. The kinetic studies show that a ternary complex $CoL{\cdot}H_2AB{\cdot}O_2$ is involved in the rate determining step. The reactions are summarised in a catalytic cycle. The kinetic data suggest that a ternary complex involving Co(3MeOsalen), triphenyl-phosphine and molecular oxygen is catalytically acive species but at higher triphenylphosphine concentrations the catalyst becomes inactive. The destruction of the catalytic activity could be due to the catalyst becoming coordinated with triphenyl phosphine at both z axis sites of the complex e.g. Co (3MeOsalen)$(PPh_3)_2$.