• 공업화학
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• 제1권2호
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• pp.215-223
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• 1990

자동차 배기가스 정화용 촉매계에서 중요하게 취급되는 CO와 NO의 산화환원반응에서 대표적인 촉매독으로 작용하는 황의 영향을 다결정 Pt 표면 위에서 초고진공계를 이용한 열탁착 분광법(TDS)을 통하여 알아보았다. Pt 표면에서의 CO와 NO의 흡착은 황에 의하여, 물리적인 흡착방해에 의한 직접적인 영향과 전자적 효과에 의한 간접적인 영향을 받았다. 800 K 이하의 온도에서 탈착하는 S는 반응활성에 큰 영향을 미치지 못하는 반면, 800 K 이상에서 탈착하는 S는 원자상태의 것으로서 반응활성에 직접적인 영향을 미쳤다. Pt 표면위에 흡착된 S는 island 형태로 존재하며, S에 의한 전자적인 영향은 주위의 모든 흡착점에 미치는 먼거리 상호작용의 경향을 나타내었다. 한편, Pt 표면에서의 CO와 NO의 반응에서 S에 의한 피독은 특정 활성점에 우선적으로 영향을 미치는 선택적인 경향을 보였다.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2018년도 춘계학술대회 논문집
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• pp.62-62
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• 2018

Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

• 대한화학회지
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• 제54권1호
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• pp.131-136
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• 2010

다양한 철 원소의 조성을 갖는 인산알루미늄 철을 합성하여 표면 성질과 벌크 성질을 조사하였다. 벤질 알코올과 디에틸 말론산의 transesterification반응에 의해 촉매 특성을 결정 하였다. 에틸 벤질 말론산과 디벤질 말론산을 유일한 생성물로 얻었다. 철 성분이 0.025 몰 퍼센트인 FeAlP의 경우에 특이한 촉매 특성과 조직상의 특성이 나타난다. 디에스터의 형성은 중간 정도 크기의 산성 자리에서 이루어진다. 물질 안에 수화된 알루미나와 polycondensed인산이 존재할 경우에는 에스터교환 반응에서 인산 알루미늄 철의 촉매 특성이 감소하게 된다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2005년도 하계학술대회 논문집 Vol.6
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• pp.552-553
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• 2005

In order to improve energy efficiency in the dilute trichloroethylene removal using the nonthermal plasma process, the barrier discharge treatment combined with manganese dioxide was experimentally studied. Reaction kinetics in this process was studied on the basis of final byproducts distribution. Decomposition efficiency was improved to about 99% at the specific energy 40J/L with passing through manganese dioxide. C=C $\pi$ bond cleavage in TCE gave DCAC (single bond, C-C) through oxidation reaction during the barrier discharge plasma treatment. Those DCAC were broken easily in the subsequent catalytic reaction due to the weak bonding energy about 3 ~ 4 eV compared with the double bonding energy in TCE molecules. Oxidation byproducts of DCAC and TCAA from TCE decomposition are generated from the barrier discharge plasma treatment and catalytic surface chemical reaction, respectively. Complete oxidation of TCE into $CO_X$ is required to about 400J/L.

• Bulletin of the Korean Chemical Society
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• 제33권5호
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• pp.1617-1621
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• 2012

The titanate nanotube (TNT) was hydrothermally synthesized in 10 M NaOH aqueous solution at $150^{\circ}C$ for 72 h. Titanate nanotube with high surface area (292 $m^2$/g) is a good candidate as a support for catalytic reaction or organic synthesis. Palladium nanoparticles with an average size of $ca$. 3 nm were well dispersed onto the surface of TNT nanotubes. Palladium loaded catalyst with high surface area shows a highly efficient ${\alpha}$ alkylation of ketones with primary alcohols.

• 공업화학
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• 제26권2호
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• pp.217-223
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• 2015

DTO (dimethyl ether to olefin) 반응에서 촉매 성능을 향상하기 위하여 염산에 의한 SAPO-34 시료의 산 처리 영향을 연구했다. 먼저 TEAOH (tetraethylammonium hydroxide)와 DEA (diethylamine)를 구조유도제로 사용하여 정육면체 형태를 갖는 균일한 크기의 SAPO-34 시료를 수열 합성했다. 제조된 촉매는 염산의 농도 및 처리 시간을 변수로 하여 개조되었다. 그 결과, 우수하게 개조된 시료는 외부 표면의 침식과 함께 총 비표면적 및 마이크로 세공부피가 증가하였으며, 산점량이 다소 감소하는 것으로 나타났다. 특히, 개조된 SAPO-0.2 M (3 h) 시료 상에서의 DTO 반응에서 촉매 수명과 경질 올레핀 선택성은 모체 SAPO-34 시료와 비교하여 크게 향상되었다. 이것은 코크 형성에 의한 비활성화가 주로 결정 외부 표면의 기공 입구에서 상대적으로 빠르게 진행된다는 것을 의미한다. 따라서 산 처리는 SAPO-34 촉매의 외부 표면을 개조함으로써 촉매의 성능을 향상할 수 있는 단순한 방법임을 확인했다.

• Korean Chemical Engineering Research
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• 제57권5호
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• pp.652-665
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• 2019

Analytical solutions of the reactant concentration inside porous spherical catalytic particles were obtained from unsteady reaction-diffusion equation by applying eigenfunction expansion method. Various surface concentrations as exponentially decaying or oscillating function were considered as boundary conditions to solve the unsteady partial differential equation as a function of radial distance and time. Dirac delta function was also used for the instantaneous injection of the reactant as the surface boundary condition to calculate average reactant concentration inside the particles as a function of time by Laplace transform. Besides spherical morphology, other geometries of particles, such as cylinder or slab, were considered to obtain the solution of the reaction-diffusion equation, and the results were compared with the solution in spherical coordinate. The concentration inside the particles based on calculation was compared with the bulk concentration of the reactant molecules measured by photocatalytic decomposition as a function of time.

• 한국수소및신에너지학회논문집
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• 제35권1호
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• pp.27-33
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• 2024

In this study, we researched Ni-based bead catalysts for the catalytic thermal decomposition of light hydrocarbons. A Ni-based bead-type catalyst was prepared, and catalytic thermal decomposition performance of light hydrocarbons was evaluated. The 30Ni/Al₂O₃ catalyst exhibited the most superior performance, with the presence of both fibrous and carbon black forms on the catalyst surface. Catalytic performance was evaluated for particles sized between 150-250 and 500 ㎛, with excellent catalytic thermal decomposition properties in the 150-250 ㎛ range. After the reaction, carbon removal through collision between catalysts in the fluidized bed was observed. It was confirmed that as the particle size increases, the amount of carbon removed increases.

• 한국재료학회지
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• 제22권6호
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• pp.316-320
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• 2012

$Co_3O_4$, $Al_2O_3$ and $Co_3O_4$/$Al_2O_3$ mesoporous powders were prepared by a sol-gel method with starting matierals of aluminum isopropoxide and cobalt (II) nitrate. A P123 template is employed as an active organic additive for improving the specific surface area of the mixed oxide by forming surfactant micelles. A transition metal cobalt oxide supported on alumina with and without P123 was tested to find the most active and selective conditions as a heterogeneous catalyst in the reaction of styrene epoxidation. A bBlock copolymer-P123 template was added to the staring materials to control physical and chemical properties. The properties of $Co_3O_4$/$Al_2O_3$ powder with and without P123 were characterized using an X-ray diffractometer (XRD), a Field-Emission Scanning Electron Microscope (FE-SEM), a Bruner-Emmertt-Teller (BET) surface analyzer, and $^{27}Al$ MAS NMR spectroscopy. Powders with and without P123 were compared in catalytic tests. The catalytic activity and selectivity were monitored by GC/MS, $^1H$, and $^{13}C$-NMR spectroscopy. The performance for the reaction of epoxidation of styrene was observed to be in the following order: [$Co_3O_4$/$Al_2O_3$ with P123-1173 K > $Co_3O_4$/$Al_2O_3$ with P123-973 K > $Co_3O_4$-973 K>$Co_3O_4$/$Al_2O_3$-973 K > $Co_3O_4$/$Al_2O_3$ with P123-1473 K > $Al_2O_3$-973 K]. The existence of ${\gamma}$-alumina and the nature of the surface morphology are related to catalytic activity.

• 공업화학
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• 제2권1호
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• pp.47-55
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• 1991

탄소침적된 수소첨가반응용 Ni 촉매의 활성재생에 관하여 연구하였다. 침적된 탄소는 여러 가지 농도의 산소로 산화시켜 제거하였으며, 촉매의 활성은 아닐린 수소첨가반응을 model 반응으로 하여 측정하였다. 탄소침적된 촉매를 산화처리할 경우 처리온도가 증가함에 따라 표면적이 증가하다가 감소하는 현상을 보였으며, 최대 표면적을 나타내는 처리온도는 처리 산소농도가 감소함에 따라 증가하였다. 처리 산소농도가 높을수록 침적탄소의 산화에 의한 반응열로 인하여 Ni 입자의 소결현상 및 담체의 기공감소가 심하게 나타났다. 5 % 산소로 처리한 촉매의 경우, 촉매의 활성이 약 90% 까지 회복되었으나 20% 산소로 처리한 촉매의 경우, 활성의 회복을 기대할 수 없었다. 5 % 산소로 재생처리할 경우, 촉매의 활성은 산화처리 시간이 증가할수록 증가하였으나, 1 시간 이후에는 거의 일정하였다.