• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.86.2-86.2
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• 2011

저온형 연료전지인 직접 메탄올 연료전지(Direct Methanol Fuel Cells, DMFC)는 친환경적인 발전 시스템, 높은 에너지 효율의 장점 때문에 주목을 받고 있으나 연료극의 촉매로 사용되는 금속은 고가의 귀금속인 Pt와 Ru가 요구되어 제조비용이 비싸기 때문에 촉매의 양을 줄이고, 반응 도중 생성되는 CO에 의한 촉매의 피독 문제 등 해결하여야 할 점이 산적해 있어 연료전지 중 촉매의 활성을 높이는 연구들이 활발히 이루어지고 있다. 종래의 MEA의 촉매층 제조공정은 우선 환원석출법에 의해 Pt-Ru/C를 합성하고 Nafion 용액에 혼합하여 Pt-Ru/C 슬러리를 제조한다. 이 방법에서는 carbon sheet에 spray 방법으로 Pt-Ru/C 촉매층이 만들어지기 때문에, Pt-Ru 촉매가 Nafion에 의해 부분적으로 매몰되어 촉매의 전기화학적 활성이 떨어지는 문제점이 있다. 이를 해결하는 방안으로 펄스전류를 이용하여 Pt-Ru 합금입자를 carbon sheet에 전기화학적으로 담지 시켜 Nafion에 매몰되는 것을 방지하는 펄스전해법 연구가 진행되고 있다. 그러나 촉매의 입자크기가 일반적으로 50~70 nm 이상으 크기 때문에 촉매의 낮은 활성이 문제점으로 야기되고 있다. 본 연구에서는 Pt-Ru/C 촉매층 제조 문제점을 해결하고, 촉매의 전기화학적 활성을 증가시키기 위해서 2~4 nm Pt-Ru 콜로이드를 전해액으로 사용하고, 전기영동법을 이용하여 Pt-Ru 나노 입자를 carbon sheet($1{\times}1cm^2$) 에 담지 시켰다. 전기영동법에서 균일한 Pt-Ru 촉매층의 제조를 위해 전류인가 방법으로는 펄스전류를 사용하였고, 실험변수로는 전해액 pH, duty cycle, 담지시간을 선정하였다. 합성된 Pt-Ru 콜로이드를 TEM분석으로 나노입자의 크기와 분산성 분석하였고, 콜로이드 나노입자의 표면전하 상태를 분석하기 위해 zeta-potential을 분석하였다. Pt-Ru/C의 촉매의 전기화학적 활성을 분석하기 위하여 0.5 M H_2SO_4$ 와 1 M $CH_3OH$ 혼합용액에 CV(Cyclic Voltammetry)실시하였고, carbon sheet 전극 상 Pt-Ru의 분산성 확인을 위하여 FE-SEM분석을 수행하였다.

• Korean Journal of Materials Research
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• v.19 no.12
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• pp.667-673
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• 2009

The electrocatalytic characteristics of oxygen reduction reaction of the $PtxM_{(1-x)}$ (M = Co, Cu, Ni) supported on multi-walled carbon nanotubes (MWNTs) have been evaluated in a Polymer Electrolyte Membrane Fuel Cell (PEMFC). The $Pt_xM_{(1-x)}$/MWNTs catalysts with a Pt : M atomic ratio of about 3 : 1 were synthesized and applied to the cathode of PEMFC. The crystalline structure and morphology images of the $Pt_xM_{(1-x)}$ particles were characterized by X-ray diffraction and transmission electron microscopy, respectively. The results showed that the crystalline structure of the Pt alloy particles in Pt/MWNTs and $Pt_xM_{(1-x)}$/MWNTs catalysts are seen as FCC, and synthesized $Pt_xM_{(1-x)}$ crystals have lattice parameters smaller than the pure Pt crystal. According to the electrochemical surface area (ESA) calculated with cyclic voltammetry analysis, $Pt_{0.77}Co_{0.23}$/MWNTs catalyst has higher ESA than the other catalysts. The evaluation of a unit cell test using Pt/MWNTs or $Pt_xM_{(1-x)}$/MWNTs as the cathode catalysts demonstrated higher cell performance than did a commercial Pt/C catalyst. Among the MWNTs-supported Pt and $Pt_xM_{(1-x)}$ (M = Co, Cu, Ni) catalysts, the $Pt_{0.77}Co_{0.23}$/MWNTs shows the highest performance with the cathode catalyst of PEMFC because they had the largest ESA.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.4
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• pp.415-423
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• 2011

HI decomposition step certainly demand catalytic reaction for efficient production of hydrogen in SI process. Platinum catalyst can apply to HI decomposition reaction as well as hydrogenation or dehydrogenation. Generally, noble metal is used as catalyst which is loaded form for getting high dispersion and wide active area. In this study, Pt was loaded onto zirconia, ceria, alumina, and silica by impregnation method. HI decomposition reaction was carried out under the condition of $450^{\circ}C$, 1atm, and $167.76h^{-1}$ (WHSV) in a fixed bed reactor for measuring catalytic activity. And property of a catalyst was observed by BET, TEM, XRD and chemisoption analysis. On the basis of experimental results, we discussed about conversion of HI according to physical properties of the loaded Pt catalyst onto each support.

• Korean Chemical Engineering Research
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• v.57 no.4
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• pp.575-583
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• 2019

The results of the catalytic reaction by pulsed injection of reactants are useful for studying the initial reaction characteristics in the case of many coke invloved reactions. The dehydrogenation characteristics of alumina supported platinum tin catalysts were investigated by pulsed injection of propane. The yield of propylene was maximized when the reduction time of propane injection catalyst was $550^{\circ}C$. Raman analysis showed that the amount of coke was very small when PtSn (4.5) catalyst was used and the short contact time was simulated by propane pulse injection. n order to differentiate the degree of dispersion of platinum, PtSn (4.5) catalyst was sintered at $900^{\circ}C$ with hydrogen, and then the temperature of air - redispersion was varied and propane pulse was injected. As a result, conversione and yield were the highest when air-redispersion temperature is $600^{\circ}C$. The lower the air-redispersion temperature, the higher the selectivity. As the tin content in the platinum catalyst increased, the propane conversion was lowered, but the selectivity to propylene increased and the yield increased. From this, it can be seen that the tin-added platinum catalyst is less active than the platinum catalyst from the beginning of the reaction, which is less affected by coke. The dehydrogenation reaction by the propane pulse injection shows a higher conversion rate than the result of continuous injection due to the formation of COx, and the amount of coke is very small. Decrease in selectivity due to the formation of COx can be reduced by increasing the reduction temperature and time.

• Journal of Environmental Science International
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• v.20 no.2
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• pp.251-260
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• 2011

$TiO_2$- and $SiO_2$-supported $Co_3O_4$, Pt and $Co_3O_4$-Pt catalysts have been studied for CO and $C_3H_8$ oxidations at temperatures less than $250^{\circ}C$ which is a lower limit of light-off temperatures to oxidize them during emission test cycles of gasoline-fueled automotives with TWCs (three-way catalytic converters) consisting mainly of Pt, Pd and Rh. All the catalysts after appropriate activation such as calcination at $350^{\circ}C$ and reduction at $400^{\circ}C$ exhibited significant dependence on both their preparation techniques and supports upon CO oxidation at chosen temperatures. A Pt/$TiO_2$ catalyst prepared by using an ion-exchange method (IE) has much better activity for such CO oxidation because of smaller Pt nanoparticles, compared to a supported Pt obtained via an incipient wetness (IW). Supported $Co_3O_4$-only catalysts are very active for CO oxidation even at $100^{\circ}C$, but the use of $TiO_2$ as a support and the IW technique give the best performances. These effects on supports and preparation methods were indicated for $Co_3O_4$-Pt catalysts. Based on activity profiles of CO oxidation at $100^{\circ}C$ over a physical mixture of supported Pt and $Co_3O_4$ after activation under different conditions, and typical light-off temperatures of CO and unburned hydrocarbons in common TWCs as tested for $C_3H_8$ oxidation at $250^{\circ}C$ with a Pt-exchanged $SiO_2$ catalyst, this study may offer an useful approach to substitute $Co_3O_4$ for a part of platinum group metals, particularly Pt, thereby lowering the usage of the precious metals.

• Journal of Sensor Science and Technology
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• v.20 no.3
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• pp.168-171
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• 2011

Porous 3C-SiC(pSiC) samples with different pore diameters were prepared from poly crystalline N-type 3C-SiC by electrochemical anodization. The pSiC surface was chemically modified by the sputtering of Pd and Pt nano-particles as a hydrogen catalyst. Changes in resistance were monitored with hydrogen concentrations in the range of 110 ppm - 410 ppm. The variations of the electrical resistance in the presence of hydrogen demonstrated that Pd and Pt-deposited pSiC samples have the ability to detect hydrogen at room temperature. Regardless of the catalyst, the 25 nm pore diameter samples showed good response and recovery properties. However, the 60 nm samples showed unstable and slow response. It was found that the pore size affects the catalyst reaction and consequently, results in changes of the sensitivity to hydrogen.

• Journal of Electrochemical Science and Technology
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• v.13 no.3
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• pp.354-361
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• 2022

In a direct methanol fuel cell system (DMFC), one of the drawbacks is methanol crossover. Methanol from the anode passes through the membrane and enters the cathode, causing mixed potential in the cell. Only Pt-based catalysts are capable of operating as cathode for oxygen reduction reaction (ORR) in a harsh acidic condition of DMFC. However, it causes mixed potential due to high activity toward methanol oxidation reaction of Pt. To overcome this situation, developing Pt-based catalyst that has methanol tolerance is significant, by controlling reactant adsorption or reaction kinetics. Pt/C decorated with phosphate ion was prepared by modified polyol method as cathode catalyst in DMFC. Phosphate ions, bonded to the carbon of Pt/C, surround free Pt surface and block only methanol adsorption on Pt, not oxygen. It leads to the suppression of methanol oxidation in an oxygen atmosphere, resulting in high DMFC performance compared to pristine Pt/C.

• 한국신재생에너지학회:학술대회논문집
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• 2008.05a
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• pp.568-571
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• 2008

A novel self-humidifying composite membrane for the proton exchange membrane fuel cell (PEMFC) at low humidity condition was developed. The Pt/$TiO_2$ catalyst particles were synthesized via supercritical impregnation methods. Pt precursor was dissolved in supercritical carbon dioxide and impregnated onto $TiO_2$ particles. Pt precursors were platinum(II) acetylacetonate, Dimethyl(1,5-cyclooctadiene) platinum(II) and we controlled the ratio of Pt to $TiO_2$. The impregnated Pt precursor was converted to $TiO_2$ supported Pt nanoparticle under various reducing conditions. Pt/$TiO_2$ catalyst particles were dispersed uniformly into the Nafion solution, and then Pt/$TiO_2$/Nafion composite membrane was prepared using solution-cast method. The self-humidifying composite membrane could minimize membrane conductivity loss under dry conditions due to the presence of catalyst and hydrophilic Pt/$TiO_2$ particles. To optimize the performance of MEA, amount of ionomer loading was controlled. And mixed catalysts were used. The cell performance of MEA was obviously improved under dry conditions at $65^{\circ}C$.

• Journal of the Korean Electrochemical Society
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• v.4 no.4
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• pp.172-175
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• 2001

Nanophase catalyst layer for direct methanol fuel cell has been fabricated by magnetron sputtering method. Catalyst metal targets and carbon were sputtered simultaneously on the Nafion membrane surface at abnormally higher gas (Ar/He mixture) pressure than that of normal thin film processing. They could be coated as a novel structure of catalyst layer containing porous PtRu or Pt and carbon particles both in nanometer range. Membrane electrode assembly made with this layer led to a reduction of the catalyst loading. At the catalyst loading of 1.5mg $PtRu/cm^2$ for anode and 1mg $Pt/cm^2$ for cathode, it could provide $45 mW/cm^2$ in the operation at 2 M methanol, 1 Bar Air at 80"C. It is more than $30\%$ increase of the power density performance at the same level of catalyst loading by conventional method. This was realized due to the ultra fine particle sizes and a large fraction of the atoms lie on the grain boundaries of nanophase catalyst layer and they played an important role of fast catalyst reaction kinetics and more efficient fuel path. Commercialization of direct methanol fuel cell for portable electronic devices is anticipated by the further development of such design.

• Journal of Powder Materials
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• v.12 no.2 s.49
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• pp.117-121
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• 2005

Platinum catalysts for the DMFC (Direct Methanol Fuel Cell) were impregnated on several carbon supports and their catalytic activities were evaluated with cyclic voltammograms of methanol electro-oxidation. To increase the activities of the Pt/C catalyst, carbon supports with high electric conductivity such as mesoporous carbon, carbon nanofiber, and carbon nanotube were employed. The Pt/e-CNF (etched carbon nanofiber) catalyst showed higher maximum current density of $70 mA cm^{-2}$ and lower on-set voltage of 0.54 V vs. NHE than the Pt/Vulcan XC-72 in methanol oxidation. Although the carbon named by CNT (carbon nanotube) series turned out to have larger BET surface area than the carbon named by CNF (carbon nanofiber) series, the Pt catalysts supported on the CNT series were less active than those on the CNF series due to their lower electric conductivity and lower availability of pores for Pt loading. Considering that the BET surface area and electric conductivity of the e-CNF were similar to those of the Vulcan XC-72, smaller Pt particle size of the Pt/e-CNF catalyst and stronger metal-support interaction were believed to be the main reason for its higher catalytic activity.