• Journal of the Korean Chemical Society
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• v.53 no.5
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• pp.499-504
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• 2009

Metals have often played important roles to some enzymatic reactions that are essential to biological processes. Therefore many scientists have studied the reaction mechanisms of catalytic reactions in metaloenzymes for many years. Methane MonoOxygenase (MMO) is an enzyme that oxidize methane to methyl alcohol. Recently Tolman et al. studied a model reaction for MMO, which is a hydroxide transfer reaction in Bis-($\mu$-oxo)-dicopper complex, and suggested several possible mechanisms. Later a two-step mechanism, which is hydrogen transfer followed by hydroxide rebound, was proposed from theoretical studies. In this study we calculated the reactant, product, and the transition state structures, and energetics of the first hydrogen transfer reaction using various DFT methods including recently developed the MO6 family of DFT, namely, MO6, MO6L, and MO6-2X. We found that the M06/6-31G(d,p)/LANL2DZ method reproduce the experimental XRD structure of reactants very well. The TS structures, barrier heights, and reaction energies depend very much on the size of the basis sets.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.306-311
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• 2016

Li-air batteries have received much attention due to their superior theoretical energy density. However, their sluggish kinetics on the cathode side is considered the main barrier to high performance. The rational design of electrode catalysts with high activity is therefore an important challenge. To solve this issue, we performed density functional theory (DFT) calculations to analyze the adsorption behavior of the $LiO_2$ molecule, which is considered to be a key intermediate in both the Li-oxygen reduction reaction (ORR) and the evolution reaction (OER). Specifically, to use the activity descriptor approach, the $LiO_2$ adsorption energy, which has previously been demonstrated to be a reliable descriptor of the cathode reaction in Li-air batteries, was calculated on $LaB_{1-x}B^{\prime}_xO_3$(001) (B, B' = Mn, Fe, Co, and Ni, x = 0.0, 0.5). Our fast screening results showed that $LaMnO_3$, $LaMn_{0.5}Fe_{0.5}O_3$, or $LaFeO_3$ would be good candidate catalysts. We believe that our results will provide a way to more efficiently develop new cathode materials for Li-air batteries.

• Journal of Korean Society for Atmospheric Environment
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• v.18 no.1
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• pp.51-58
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• 2002

Destruction process of toluene using a wire-cylindrical BBD (Dielectric Barrier Discharge) reactor packed with catalysts was investigated to characterize the synergetic effects of non-thermal plasma and catalyst process. The catalysts used in the present study were ${\gamma}$-Al$_2$BO$_3$ and Pt/${\gamma}$-Al$_2$O$_3$. Under the numerous test conditions, specific energy density (SED (J/L)) and the conversion of toluene, defined as (1 -[C$_{f}$]/[C$_{i}$]), were measured. The test results showed that toluene decomposition efficiency followed the pseudo-first order in the case of plasma only process. The pseudo-first order process, however, was modified to pseudo-zeroth order reaction in the case of catalyst-assisted plasma process. This modification of the reaction order was verified based on a simple kinetic model proposed in the present study. Owing to the modification of reaction order, which resulted from the catalytic process, the specific energy to achieve the high removal efficiencies, i.e. 80~90%, was reduced significantly.y.y.

• Journal of Korean Society for Atmospheric Environment
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• v.16 no.3
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• pp.247-256
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• 2000

Basic characteristics of non-thermal plasma process to remove C2H4 and NO have been experimentally investigated with a packed-bed type reactor and an ac power supply. The performance of the non-thermal plasma generated by ac power supply was compared with that of a wire-plate type reactor equipped with a pulsed power supply. The result shows that the non-thermal plasma can be effectively generated with an AC power supply that can be easily fabricated with conventional techniques. In order to understand the basic reaction mechanisms of the non-thermal plasma process, parametric tests for different carrier gases(air and nitrogen) and for different reaction pathways have been performed. The test results show that O3 generated by non-thermal plasma plays an dominant role to oxidize C2H4 and NO over N and O radicals when these pollutant gases are carried by dry air under room temperature condition. Experimental observations, however, indicate that N and O radicals can significantly affect on the removal process of the pollutant gases under certain conditions.

• Nuclear Engineering and Technology
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• v.47 no.6
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• pp.662-668
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• 2015

A suspension of titanium nanoparticles (Ti NPs) in liquid sodium (Na) has been proposed as a method to mitigate the violent sodium-water reaction (SWR). The interparticle potential between Ti NPs in liquid Na may play a significant role in the agglomeration of NPs on the reaction surface and in the bulk liquid Na, since the potential contributes to a reduction in the long-term dispersion stability. For the effective control of the SWR with NPs, a physical understanding of the molecular dynamics of NPs in liquid Na is key. Therefore in this study, the nonretarded Van der Waals model and the solvation potential model are employed to analyze the interparticle potential. The ab initio calculation reveals that a strong repulsive force driven by the solvation potential exceeds the interparticle attraction and predicts the agglomeration energy required for two 10-nm Ti NPs to be $4{\times}10^{-17}J$. The collision theory suggests that Ti NPs can be effective suppressors of the SWR due to the high energy barrier that prevents significant agglomeration of Ti NPs in quiescent liquid Na.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.152-152
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• 2013

Mechanism of energy conversion from chemical to electrical during exothermic catalytic reactions at the metal surfaces has been a fascinating and crucial subject in heterogeneous catalysis. A metal-semiconductor Schottky nanodiode is novel device for direct detection of chemically induced hot electrons which have sufficient energy to surmount the Schottky barrier. We measured a continuous chemicurrent during the hydrogen oxidation under of 760 Torr of O2 and 6 Torr of H2 by using Pt/Si and Pt/TiO2 nanodiodes at reaction temperatures and compared the chemicurrent with the reaction turnover rate. The thermoelectric current was measured by carrying out an experiment under O2 condition for elimination of the background current. Gas chromatograph and source meter were used for measurement of the chemical turnover rate and the chemicurrent, respectively. The correlation between the chemicurrent and the chemical turnover rate under hydrogen oxidation implies how hot electrons generated on the metal surface affect hydrogen oxidation.

• Korean Journal of Materials Research
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• v.32 no.8
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• pp.339-344
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• 2022

The lattice oxygen mechanism (LOM) is considered one of the promising approaches to overcome the sluggish oxygen evolution reaction (OER), bypassing -OOH^* coordination with a high energetic barrier. Activated lattice oxygen can participate in the OER as a reactant and enables O^*-O^* coupling for direct O₂ formation. However, such reaction kinetics inevitably include the generation of oxygen vacancies, which leads to structural degradation, and eventually shortens the lifetime of catalysts. Here, we demonstrate that Se incorporation significantly enhances OER performance and the stability of NiFe (oxy)hydroxide (NiFe) which follows the LOM pathway. In Se introduced NiFe (NiFeSe), Se forms not only metal-Se bonding but also Se-oxygen bonding by replacing oxygen sites and metal sites, respectively. As a result, transition metals show reduced valence states while oxygen shows less reduced valence states (O^-/O₂^2-) which is a clear evidence of lattice oxygen activation. By virtue of its electronic structure modulation, NiFeSe shows enhanced OER activity and long-term stability with robust active lattice oxygen compared to NiFe.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.11
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• pp.1146-1153
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• 2008

Numerical simulation was carried out to study the trichloroethylene (TCE) degradation by permeable reactive barrier (PRB), and revealed the effect of concentration of TCE, iron medium mass, and concentration of iron-reducing bacteria (IRB). Newly developed model was based on axial dispersion reactor model with chemical and biological reaction terms and was implemented using MATLAB ver R2006A for the numerical solutions of dispersion, convection, and reactions over column length and elapsed time. The reaction terms include reactions of TCE degradation by zero-valent iron (ZVI, Fe$^0$) and ferrous iron (Fe$^{2+}$). TCE concentration in the column inlet was maintained as 10 mg/L. Equation for Fe$^0$ degradation includes only TCE reaction term, while one for Fe$^{2+}$ has chemical and biological reaction terms with TCE and IRB, respectively. Two coupled equations eventually modeled the change of TCE concentration in a column. At Fe$^0$ column, TCE degradation rate was found to be more than 99% from 60 hours to 235 hours, and declined to less than 1% in 1,365 hours. At the Fe$^{2+}$ and IRB mixed column, TCE degradation rate was equilibrated at 85.3% after 210 hours and kept it constant. These results imply that the ferrous iron produced by IRB has lowered the TCE degradation efficiency than ZVI but it can have higher longevity.http://kci.go.kr/kciportal/ci/contents/ciConnReprerSearchPopup.kci#

• Proceedings of the KIEE Conference
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• 1999.07d
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• pp.1974-1976
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• 1999

The dynamic behavior so fsaturaed-fatty acids $C_{16},\;C_{18},\;C_{20}$ and 8A5H were measured by displacement current method when a barrier was compressed and expanded. I-A, $\pi-A$ isotherms of $C_{16},\;C_{18},\;C_{20}$ were similar, but $C_{20}$ was bad relatively. 8A5H showed the form of double liquid films and had an reversible reaction when a barrier was compressed and then expanded.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.72-72
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• 2010

Recent development of organic solar cell approaches the level of 8% power conversion efficiency by the introduction of new materials, improved material engineering, and more sophisticated device structures. As for interface engineering, various interlayer materials such as LiF, CaO, NaF, and KF have been utilized between Al electrode and active layer. Those materials lower the work function of cathode and interface barrier, protect the active layer, enhance charge collection efficiency, and induce active layer doping. However, the addition of another step of thin layer deposition could be a little complicated. Thus, on a typical solar cell structure of Al/P3HT:PCBM/PEDOT:PSS/ITO glass, we used Li:Al alloy electrode instead of Al to render a simple process. J-V measurement under dark and light illumination on the polymer solar cell using Li:Al cathode shows the improvement in electric properties such as decrease in leakage current and series resistance, and increase in circuit current density. This effective charge collection and electron transport correspond to lowered energy barrier for electron transport at the interface, which is measured by ultraviolet photoelectron spectroscopy. Indeed, through the measurement of secondary ion mass spectroscopy, the Li atoms turn out to be located mainly at the interface between polymer and Al metal. In addition, the chemical reaction between polymer and metal electrodes are measured by X-ray photoelectron spectroscopy.