• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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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.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2002.04a
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• pp.114-117
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• 2002

Sorption and desorption studies were conducted to evaluate several media as a potential biobarrier for the remediation of groundwater contaminated with hydrophobic organic compounds (HOCs). Pahokee and Bion peats, Devonian Ohio shale, vermicompost, and 50% HDTMA-montmorillonite were used as model sorbents. Sorption and desorption isotherms were determined using the radiolabeled phenanthrene (Phe). Sorption capacity of Phe on several sorbents was in the order Ohio shale > 50% HDTMA-montmorillonite > vermicompost > Pahokee peat. Mineralization kinetics was investigated for Phe-sorbed sorbents using Pseudomonas putida 17484. Among the tested sorbents, active biodegradation of Phe was observed in shale and vermicompost: degradation in shale exhibited little lag time while that in shale showed a significant lag time. Results of this study indicate that sorbents used in this work can be utilized as permeable reactive biobarrier media for the remediation of HOC-contaminated groundwater.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.360-360
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• 2010

Very initial stage of oxidation process of Si (001) surface was investigated using large scale molecular dynamics simulation. Reactive force field potential was used for the simulation owing to its ability to handle charge variation associated with the oxidation reaction. To know the detail mechanism of both adsorption and desorption of water molecule (for simulating wet oxidation), oxygen molecule (for dry oxidation) and their atom constituents, interaction of one molecule with Si surface was carefully observed. The simulation is then continued with many water and oxygen molecules to understand the kinetics of oxide growth. The results show that possibilities of desorption and adsorption depend strongly on initial atomic configuration as well as temperature. We observed a tendency that H atoms come relatively into deeper surface or otherwise quickly desorbed away from the silicon surface. On the other hand, most oxygen atoms are bonded with first layer of silicon surface. We also noticed that charge transfer is only occur in nearest neighbor regime which has been pointed out by DFT calculation. Atomic structure of the interface between the oxide and Si substrate was characterized in atomic scale.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2004.04a
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• pp.186-191
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• 2004

Sorption kinetics of 2-chlorophenol(2-ChP), 2,4-dichlorophenol(2,4-DChP) and 2,4,5-trichlorophenol (2,4,5-TChP), onto montmorillonite modified with hexadecyltrimethyl ammonium cations(HDTMA-mont) were investigated. One-site mass transfer model(OSMTM) and two compartment first-order kinetic model(TCFOKM) were used to analyze kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM in describing sorption and desorption kinetics of chlorophenols in HDTMA-mont. For all chlorophenols, the results of OSMTM analysis indicate that the predominant deprotonated speciation(at pH 9.15) exhibited higher mass transfer coefficient( $k_{s}$ ) than the protonated speciation(at pH 4.85). This is because the deprotonated speciation has stronger hydrophobic interaction than protonated speciation. Most sorption completes in three hours. The fraction of the fast sorption and the first-order sorption rate constants for the fast and slow compartments in TCFOKM were determined by fitting experimental data to the TCFOKM. The results of kinetics reveal that the fraction of the fast sorption( $f_1$) and the sorption rate constants in the fast compartments( $k_1$) were in the order 2,4,5-TChP > 2,4-DChP > 2-ChP, which agrees with the magnitude of the $K_{ow}$ . The first-order sorption rate constants in the fast compartment(10$^{0.8}$ - 10$^{1.22}$ h $r^{-1}$ ) were much larger than those in the slow compartment(10$^{-1}$.74/ - 10$^{-2}$.622/ h $r^{-1}$ ).> ).).

• Journal of Hydrogen and New Energy
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• v.8 no.3
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• pp.101-109
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• 1997

We propose a new concept of hydrogen absorbing alloy, "Laves phase related BCC solid solution". It was firstly found among the phases tormed in multicomponent nominal $AB_2$ alloys which consisted of Zr and Ti for the A metal site and 5A, 6A and 7A transition metals for the B metal sites. In these alloys a BCC solid solution often coexisted with a Laves phase. It showed stability of hydrides and reaction kinetics almost identical to intermetallics such as Laves phase alloys. We prepared an almost pure "Laves phase related BCC solid solution" and found that it had a large hydrogen capacity (more than 2 mass%) and fast hydrogen absorption and desorption kinetics at ambient temperature and pressure. This new hydrogen absorbing alloy may open a new era of hydrogen related application such as hydrogen vehicles.

• 한국생물공학회:학술대회논문집
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• 2000.04a
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• pp.418-421
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• 2000

A model was developed to describe the microbial decontamination of diesel contaminated soil in a soil column. The biodegradation rate of diesel in nature depends on temperature and the pH of soil, availability of nutrients, oxygen and water. The soil moisture content is one of the essential factors because it characterizes the availability not only of water to microorganisms but also of oxygen and nutrient dissolved in soil. In this work, the rate of biodegradation was modeled by coupling Michaelis-Menten kinetics for the aqueous-phase solute with adsoption-desoption equation for diesel sorption and desorption from soil.

• Proceedings of the Materials Research Society of Korea Conference
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• 1998.08a
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• pp.145.1-145
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• 1998

• Journal of Hydrogen and New Energy
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• v.22 no.4
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• pp.458-464
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• 2011

Recently, one of the hydrogen production methods has attracted using dense metallic membrane. It has high hydrogen permeation and selectivity which hardly could adopt industrial product because of high cost, hydrogen embrittlment and thermal stability. Meanwhile, vanadium has high hydrogen solubility and it use to instead of Pd-Ag amorphous membrane. Aluminum carried out blocking hydrogen diffusion on grain boundary therefore protecting hydrogen embrittlement. Most of dense metallic membrane is solution diffusion mechanism. The solution diffusion mechanism was very similar hydrogen storing steps such as steps of metal hydride. Thus, V-Al composites were fabricated to use hydrogen induced mechanical alloying. The fabricated V-Al composites were characterized by XRD, SEM, EDS and simultaneous TG/DSC analyses. The hydrogenation behaviors were evaluated using a Sievert's type automatic PCT apparatus. The hydrogenation behaviors of V-Al composites was evaluated too low hydrogen stored capacity and fast hydrogenation kinetics. In PCI results, V-Al composites had low hydrogen solubility, in spite of that, hydrogen kinetics was calculated very fast and hydrogen absorption/desorption contents were same capacity.

• Transactions of the Korean Society of Automotive Engineers
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• v.14 no.3
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• pp.125-132
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• 2006

Transient kinetics of $NH_3$ adsorption/desorption and of SCR(selective catalytic reduction) of NO with $NH_3$ were studied over vanadium based catalysts, such as $V_2O_5/TiO_2$ and $V_2O_5-WO_3/TiO_2$. In the present catalytic reaction process, NO adsorption is neglected while $NH_3$ is strongly chemisorbed on the catalytic surface. Accordingly, it is ruled out the possibility of a reaction between strongly adsorbed $NH_3$ and NO species in line with the hypothesis of an Eley-Rideal mechanism. The present kinetic model assumes; (1) non-activated $NH_3$ adsorption, (2) Temkin-type $NH_3$ coverage dependence of the desorption energy, (3) non-linear dependence of the SCR reaction rate on the $NH_3$ surface coverage. Thus, the surface heterogeneity for adsorption/desorption of $NH_3$ is taken into account in this model. The present study extends the pure chemical kinetic model based on a powdered-phase catalytic system to the chemico-physical one applicable to a realistic monolith reactor.

• Journal of Hydrogen and New Energy
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• v.21 no.2
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• pp.81-88
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• 2010

Hydrogen energy applications have recognized clean materials and high energy carrier. Accordingly, Hydrogen energy applies for fuel cell by Mg and Mg-based materials. Mg and Mg-based materials are lightweight and low cost materials with high hydrogen storage capacity. However, commercial applications of the Mg hydride are currently hinder by its high absorption/desorption temperature, and very slow reaction kinetics. Therefore one of the most methods to improve kinetics focused on addition transition metal oxide. Addition to transition metal oxide in $MgH_x$ powder produce $MgH_x$-metal oxide composition by mechanical alloy and it analyze XRD, EDS, TG/DSC, SEM, and PCT. This report considers kinetics by transition metal oxide rate and Hydrogen pressure. In this research, we can see behavior of hydriding/dehydriding profiles by addition catalyst (transition metal oxide). Results of PCI make a excellent showing $MgH_x$-5wt.% Sc2O3 at 623K, $MgH_x$-10wt.% $Sc_2O_3$ at 573K.