• Transactions of the Korean hydrogen and new energy society
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• v.23 no.4
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• pp.346-352
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• 2012

The properties of methane oxidation were studied in this research over transition metal containing $CeO_2$ (TM/$CeO_2$, TM=Ni, Co, Cu, Fe) with TM content of 5 wt. % at atmospheric pressure. The characteristics of catalysts were investigated by various characterization techniques, including XRD, GC, SEM and EPMA analyses. The catalytic tests were carried out in a fixed Rmix ratio of 1.5 ($CH_4/O_2$) in a fixed-bed reactor operating isothermally at atmospheric pressure. Only the Ni/$CeO_2$ catalysts showed syngas production above $400^{\circ}C$ via typical partial oxidation reaction whereas other catalysts induced complete oxidation resulting in the production of $CO_2$ and $H_2O$ in whole reaction temperature range. From the quantitative analysis on carbon deposition after catalytic tests, Cu/$CeO_2$ was found to show the highest resistance on carbon deposition. Therefore Cu can be proposed as an efficient catalyst element which can be combined with a conventional Ni-based SOFC anode to enhance the carbon tolerance.

• Applied Chemistry for Engineering
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• v.9 no.3
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• pp.355-360
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• 1998

Reduction activity of precious metal-loaded HZSM-5 for NO has been studied and was compared to that of Cu-HZSM-5 in the presence of excess oxygen. It was found that among the catalysts used in this study, Ru-HZSM-5 was the most active catalyst for the reduction of NO to $N_2$ in the absence of hydrocarbon reductant. The highest conversion obtained was 45%. No severe inhibition of water vapor to the reduction was observed. It is suggested that the higher catalytic activity of Ru-HZSM-5 may result from the better ability to oxidize NO to $NO_2$ in the presence of excess oxygen. A proposed reaction mechanism for the reduction of NO to $N_2$ in the presence of excess oxygen is that NO is oxidized to $NO_2$ on the surface of Ru-HZSM-5 catalyst and the adsorbed $NO_2$ on the surface is then decomposed to $N_2$. $NO_2$ is supposed to the reaction.

• Applied Chemistry for Engineering
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• v.7 no.2
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• pp.261-268
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• 1996

Various $Cu/SiO_2$ catalysts with copper concentration ranging from 0 to 50wt% were prepared by kneading method for the steam reforming of methanol. These catalysts were calcined at temperatures in the range of $400^{\circ}C{\sim}900^{\circ}C$ and then reduced in a $H_2$ atmosphere in the range of $150^{\circ}C{\sim}350^{\circ}C$. Steam reforming of methanol was carried out at atmospheric pressure over a temperature range of $200^{\circ}C{\sim}400^{\circ}C$, steam/methanol molar ratio of 0.4~1.6 and W/F of 3~25 g.-cat.hr./mol. Characterization of the catalysts was studied using IR, BET and XRD. Using copper nitrate as a precursor for catalysts, pH in the preparation of catalysts had a great effect on the catalytic activity, but pH in the preparation of catalysts, calcination temperature, and reducing temperature in $H_2$ atmosphere had no effect on the product distribution. Optimum copper concentration, calcination temperature and reducing temperature were 40wt%, $700^{\circ}C$ and $300^{\circ}C$, respective)y. Reaction temperature for maximum $H_2$ production was $275^{\circ}C$, and the formation of methane which lowered quantity and quality of $H_2$ would be inhibited below $275^{\circ}C$. $Cu^{\circ}-Cu_2O$ might be active species in $Cu/SiO_2$ catalyst.

• Applied Chemistry for Engineering
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• v.20 no.4
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• pp.381-385
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• 2009

A basic objective is the preparation and surface studies of supported molten salt catalysts because molten salts can stay as the liquid phase in the range of the ordinary reaction temperature. Many kinds of metal salt mixtures for the formation of molten salt phase are appliable but CuCl and KCl were selected in this study because Cu is considered catalytically reactive in many reactons. The loading of the molten salt was selected as 25 vol% of the total pore volume of ${\gamma}-alumina$ to provide reasonable exposed surface area. The surface structure of catalysts containing molten salts in the ${\gamma}-alumina$ was studied using scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). CuCl and KCl were added into the ${\gamma}-alumina$ using concentrated hydrochloric acid solution by the impregnation technique. The surfaces of the prepared catalysts before and after heat treatments were compared and they suggested that the heat treatment of catalysts helped the formation of molten-salt although the surface compositions of CuCl and KCl were not uniform.

• Journal of the Korea Institute of Military Science and Technology
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• v.3 no.1
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• pp.164-175
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• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• Applied Chemistry for Engineering
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• v.17 no.2
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• pp.125-131
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• 2006

Dimethyl ether (DME) is a new clean fuel as an environmentally-benign energy resource. DME can be manufactured from various energy sources including natural gas, coal, biomass and spent plastic. In addition to its environmentally friendly properties, DME has similar characteristics to those of LPG. Therefore, it is considered as an excellent substitute fuel for LPG, fuel cells, power plant, and especially diesel and is expected to be the alternative fuel by 2010. The experimental study of the direct synthesis of DME was investigated under various conditions over a temperature range of $220{\sim}280^{\circ}C$, syngas ratio 1.2~3.0. All experiments were carried out with a hybrid catalyst, composed of a methanol synthesis catalyst ($Cu/ZnO/Al_2O_3$) and a dehydration catalyst (${\gamma}-Al_2O_3$). The observed reaction rate follows qualitatively a Langmiur-Hinshellwood model as the reaction mechanism. Such a mechanism is considered with three reactions; methanol synthesis, methanol dehydration and water gas shift reaction. From a surface reaction with dissociative adsorption of hydrogen, methanol, and water, individual reaction rate was determined.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.110.1-110.1
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• 2010

A bench scale slurry bubble column reactor (SBCR) with active-Fe based catalyst was developed for the Fischer-Tropsch synthesis (FTS) reaction. Considering the highly exothermic reaction heat generated in the bench scale SBCR, an effective cooling system was devised consisting of a U-type dip tube submerged in the reactor. Also, the physical and chemical properties of the catalyst were controlled so as to achieve high activity for the CO conversion and liquid oil ($C_{5+}$) production. Firstly, the FTS performance of the FeCuK/$SiO_2$ catalyst in the SBCR under reaction conditions of $265^{\circ}C$, 2.5 MPa, and $H_2/CO=1$ was investigated. The CO conversion and liquid oil ($C_{5+}$) productivity in the reaction were 88.6% and 0.226 $g/g_{cat}-h$, respectively, corresponding to a liquid oil ($C_{5+}$) production rate of 0.03 bbl/day. To investigate the FTS reaction behavior in the bench scale SBCR, the effects of the space velocity and superficial velocity of the synthesis gas and reaction temperature were also studied. The liquid oil production rate increased upto 0.057 bbl/day with increasing space velocity from 2.61 to 3.92 $SL/h-g_{Fe}$ and it was confirmed that the SBCR bench system developed in this research precisely simulated the FTS reaction behavior reported in the small scale slurry reactor.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.97.1-97.1
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• 2011

저온에서 양이온 고분자막을 사용하는 고분자 연료전지의 경우 뛰어난 성능과 다양한 응용분야로 인해 많은 연구와 실증이 이루어지고 있지만 공기극에서의 느린 산소 환원반응으로 인해 백금과 같은 귀금속의 사용이 불가피하고 백금의 제한된 매장량과 높은 가격으로 인해 상용화가 늦어지고 있다. 그래서 많은 연구자들이 합금 촉매 또는 비귀금속 촉매를 이용한 전극 개발에 집중하고 있다. 알칼리 분위기에서 저가의 전이 금속들이 백금과 비슷한 활성을 보이고 고체 음이온 교환막이 개발됨에 따라 최근 알칼리 연료전지가 다시금 큰 주목을 받고 있다. 그러나 고분자 연료전지와는 달리 아직 촉매나 전해질막, 이오노머의 특성 및 메커니즘에 관해 별로 알려진 것이 없다. 본 연구에서는 직접 개발한 세공충진막 형태의 탄화수소계의 음이온 교환막과 비귀금속 공기극 촉매를 이용하여 막전극접합체(MEA)를 개발하였고 촉매 및 이오노머 함량과 같은 전극 조성, 막전극접합체의 제조 및 체결, 가습이나 가스조성 등의 단위전지 운전조건과 같은 다양한 변수에 대해에 최적 조건을 도출하고자 하였다. 공기극 촉매는 Cu-Fe/C를 이용한 상용 촉매를 이용하였고 이오노머의 경우는 탄화수소계의 상용 제품을 사용하였으며 음이온 교환막에 전극층을 형성하기 위해서는 스프레이 공정을 이용하였다. 단위전지를 통해 성능을 확인하였고 임피던스 및 CV를 통해 전기화학적인 특성을 규명하였다. 조건의 최적화를 통해 상당한 성능 향상을 이루었으나 추가적인 성능 향상 및 내구성 확보 등에 대해 계속적인 실험을 진행할 예정이다.

• Journal of the Korean institute of surface engineering
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• v.55 no.3
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• pp.180-186
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• 2022

The production of hydrogen via water electrolysis (i.e., green hydrogen) using renewable energy is key to the development of a sustainable society. However, most current electrocatalysts are based on expensive precious metals and require the use of highly purified water in the electrolyte. We demonstrated the preparation of a non-precious metal catalyst based on CuCo₂O₄ (CCO) via simple electrodeposition. Further, an optimization process for electrodeposition potential, solution concentration and electrodeposition method was develop for a catalyst-substrate integrated electrode, which indicated the highly electrocatalytic performance of the material in electrochemical tests and when applied to an anion exchange membrane water electrolyzer.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.2
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• pp.163-169
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• 2005

Photocatalytic oxidation of Cu(II)-EDTA has been studied using solar/$TiO_2$ photocatalysis as an energy source. Photocatalysis efficiency on the treatment of Cu(II)-EDTA was investigated using different types of solar collectors as well as by variation of the angles of solar collector solar light intensities, flow rates, and areas of solar collector. effect of $H_2O_2$ and types of $TiO_2$ catalyst on the treatment of Cu(II)-EDTA was also investigated. Removal of Cu(II) and DOC was favorable with a hemispherical collector than with a flat collector Removal of Cu(II) and DOC increased with increasing angles of solar collector up to $38^{\circ}$. Slurry type $TiO_2$ showed four-times higher removal efficiency than immobilized type $TiO_2$. Removal of both Cu(II) and DOC at a clear sky of solar light intensity ranging from 0.372 to $2.265\;mW/cm^2$ was greater than removal at a cloudy day of solar light intensity ranging from 0.038 to $1.129\;mW/cm^2$. From the result of this research that the removal efficiency of Cu(II) and DOC increased as the solar light intensity increased, it can be inferred that quantum yield in the destruction of Cu(II)-EDTA may directly related with the solar light intensity. Removal of Cu(II) increased as increasing the area of solar collector and was similar at lower flow rates white removal of Cu(II) was interfered at higher flow rates. When immobilized $TiO_2$ was used, removal efficiency of Cu(II) increased in the presence of $H_2O_2$ while negligible effect was found in the use of $TiO_2$ slurry.