• 조명전기설비학회논문지
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• 제20권2호
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• pp.45-49
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• 2006

본 논문은 마이크로 전극 시스템에 의하여 연료전지 및 Ni-MH 전지로의 응용을 가정한 $AB_5$계 수소저장합금인 $MmNi_{3.55}Co_{0.75}Mn_{0.4}Al_{0.3}$의 단일 입자에 대하여 전기화학적인 평가를 수행하였다. 즉 Carbon fiber 마이크로 전극을 합금 입자 한개 위에 전기적인 접촉을 이루도록 조정하고, 합금 입자 내에서 수소원자의 겉보기 화학적 확산계수를 계산하기 위하여 Potential-Step 실험을 실시하였다. 여기에서 사용되는 합금입자는 치밀하고 전도성이 있는 구형이므로 데이터 해석을 위해 구형확산 모델을 적용하였다. 실험결과로서 겉보기 확산계수($D_{app}$)는 수소 흡장 및 방출되는 전 과정에서 $10^{-9}$과 $10^{-10}[cm^2/s]$ 수준인 것으로 확인되었다. 마이크로 전극 측정 시스템에 의한 단일 입자의 전기화학적 평가는 기존의 Composite Film 전극에 비해 수소저장합금에 대해 보다 상세하고 정확한 정보를 쉽게 얻을 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제28권4호
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• pp.529-532
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• 2007

Combined temperature programmed reaction (TPR) and infrared (IR) spectroscopic studies for Fischer- Tropsch reaction have been performed over Ru/SiO2 and Ru-Ag/SiO2 supported catalysts. Reaction of linearly absorbed CO with hydrogen starts at 375 K over Ru/SiO2 catalyst and reaches maximum at 420 K accompanied with an intensity decrease of linear CO absorption. The reaction with bridged absorbed CO peaks around 510-535 K. Addition of Ag yields mixed Ru-Ag bimetallic sites while it suppresses the formation of bridged bonded CO. Formation of methane on this modified surface occurs at 390 K and reaches maximum at 444 K. Suppression of hydrogen on the Ag-doped surface also occurs resulting in the formation of unsaturated hydrocarbons and of CHx intermediates not observed with Ru/SiO2 catalyst. Such intermediates are believed to be the building blocks of higher hydrocarbons during the Fischer-Tropsch synthesis. Linearly absorbed CO is found to be more reactive as compared to bridged CO. The Ag-modified surface also produces CO2 and carbon. On this surface, hydrogenation of CO begins at 390 K and reaches maximum at 494 K. The high temperature for hydrogenation of absorbed CO and C over Ru-Ag/SiO2 catalyst as compared to Ru/SiO2 catalyst is due to the formation of Ru-Ag bimetallic surfaces impeding hydrogen adsorption.

• 한국수소및신에너지학회논문집
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• 제7권2호
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• pp.147-155
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• 1996

지구온난화를 방지하기 위하여 대기중에 방출되는 이산화탄소를 고정화시키는 기술의 하나로 이산화탄소를 접촉수소화시키는 연구를 수행하였다. 수소화 촉매로는 $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$를 기본으로 하여 여기에 팔라듐을 추가한 촉매들을 이용하였으며, 200서 $350^{\circ}C$ 사이의 온도에서 상압 및 고압의 조건에서 수소화 반응을 행하였다. 그 결과 수소화 반응에 가장 적합한 반응조건은 반응온도 $250^{\circ}C$, 반응압력 30기압 이상에서 메탄올의 선택도와 수율이 제일 좋았다. 그러나 예상한 바와는 달리 팔라듐의 첨가에 의한 반응성의 향상은 없었다.

• Bulletin of the Korean Chemical Society
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• 제20권9호
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• pp.993-998
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• 1999

The concurrent production of methanol and dimethyl ether from carbon dioxide hydrogenation has been studied under various reaction conditions. First, the methanol synthesis was compared with the concurrent production method. For the methanol synthesis, the ternary mixed oxide catalyst (CuO/ZnO/Al2O3) was used and for the coproduction of methanol and dimethyl ether, silica-alumina was mixed with the methanol synthesis catalyst to be a hybrid catalyst. The results show that the co-production provides much higher per-pass yield than methanol synthesis even at very short contact time. The effects of temperature, contact time, pressure and catalyst hybrid ratio on the product yields and selectivities were also determined in the co-production.

• Bulletin of the Korean Chemical Society
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• 제8권4호
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• pp.324-328
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• 1987

Reaction of Rh $(ClO_4)(CO)(PPh_3)_2$ (1) with trans-$C_6H_5CH = CHCH_2OH$ (2) produces a new cationic rhodium(Ⅰ) complex, $[Rh(trans-C_6H_5CH = CHCHO)(CO)(PPh_3)_2]ClO_4$ (3) where 2 is coordinated through the oxygen atom but not through the olefinic group. At room temperature under nitrogen, complex 1 catalyzes dehydrogenation, hydrogenolysis, and isomerization of 2 to give $trans-C_6H_5CH$ = CHCHO (4), trans-$C_6H_5CH = CHCH_3$ (5) and $C_6H_5CH_2CH_2CHO$ (6), respectively, and oligomerization of 2 whereas under hydrogen, complex 1 catalyzes hydrogenation of 2 to give $C_6H_5CH_2CH_2CH_2OH$ (7) and hydrogenolysis of 2 to 5 which is further hydrogenated to $C_6H_5CH_2CH_2CH_3$ (8). The dehydrogenation and hydrogenolysis of 2 with 1 suggest an interaction between the rhodium and the oxygen atom of 2, whereas the isomerization and hydrogenation of 2 with 1 indicate an interaction between the rhodium and the olefinic system of 2.

• 공업화학
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• 제20권2호
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• pp.201-207
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• 2009

Dodecanol 합성을 위한 methyl dodecanoate의 수소화반응을 위하여 copper chromite를 세라믹법, 공침법 및 개량된 공침법으로 합성하였다. 입자의 형상은 SEM 및 XRD로 확인하였으며 수소화 반응후 얻어진 생성물은 GC, GC/MSD 및 NMR로 분석하였다. 합성된 입자는 (1) 3.2에서 $7.0{\mu}m$ 크기의 구형형태(세라믹법), (2) 50에서 500 nm 크기의 구형이 혼재한 판형태(공침법) 및 (3) 작고 균일한 구형형태(개량된 공침법)를 보였다. 입자의 크기를 제어하기 위하여 PEG, Span 80 및 polyacrylate등 다양한 분산제 용액에서 copper chromite를 합성하였다. PEG (Mw = 4000) 수용액에서 합성한 입자가 30~50 nm 크기로 가장 작고 균일하였으며, $280^{\circ}C$ 및 100 atm에서 촉매의 반응성을 테스트한 결과, dodecanol의 수율은 79.9%로 얻어졌다. 수소화반응에서 촉매의 반응성은 촉매의 크기가 작고 균일할수록 높아지는 경향을 보였다. 최적화된 반응조건인 $280^{\circ}C$ 및 240 atm에서 dodecanol의 수율은 95.5%였다.

• Bulletin of the Korean Chemical Society
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• 제16권6호
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• pp.524-528
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• 1995

The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

• Bulletin of the Korean Chemical Society
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• 제19권4호
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• pp.466-470
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• 1998

Catalytic hydrogenation of carbon dioxide for the simultaneous synthesis of methanol and dimethyl ether (together called oxygenates) over a combination of methanol synthesis and methanol dehydration catalysts has been studied. Various methanol synthesis and methanol dehydration catalysts were examined for this reaction. The addition of promotors like $Ga_2O_3\; and\; Cr_2O_3$ to Cu/ZnO catalyst gave much more enhanced yield on the formation of oxygenates. From the results, the promotional effect of $Cr_2O_3$ has been explained in terms of increase in the intrinsic activity of Cu while that of $Ga_2O_3$ being increase in the dispersion of Cu. Among the methanol dehydration catalysts examined, the solid acids bearing high population of intermediate-strength acid sites were found to be very effective for the production of oxygenates. HY zeolite which contains strong acid sites produce small amount of hydrocarbons as by-products. However, CuNaY zeolite in which the presence of strong acid sites are minimum gives very high oxygenates yield without the formation of hydrocarbons.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2349-2356
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• 2014

The recycling technology by the catalytic conversion is one of the most promising techniques for the $CO_2$ treatment of coal burning power plant flue gases. The conversion of $CO_2$ to valuable product of $CH_4$ can be used as a fuel to run the turbine for electricity generation. Through this technique, the amount of coal needed for the combustion in a gas turbine can be reduced as well as $CO_2$ emissions. Therefore, a series of catalysts based on cerium oxide doped with copper, nickel and manganese were prepared by impregnation method. From the characterization analysis, it showed that the prepared catalysts calcined at $400^{\circ}C$ were amorphous in structure with small particle size in the range below 100 nm. Meanwhile, the catalyst particles were aggregated and agglomerated with higher surface area of $286.70m^2g^{-1}$. By increasing the calcination temperature of catalysts to $1000^{\circ}C$, the particle sizes were getting bigger (> 100 nm) and having moderate crystallinity with lower surface area ($67.90m^2g^{-1}$). From the catalytic testing among all the prepared catalysts, Mn/Ce-75/$Al_2O_3$ calcined at $400^{\circ}C$ was assigned as the most potential catalyst which gave 49.05% and 56.79% $CO_2$ conversion at reaction temperature of $100^{\circ}C$ and $200^{\circ}C$, respectively.

• Korean Chemical Engineering Research
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• 제44권4호
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• pp.363-368
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• 2006

$C_9$-알데히드를 수소화하여 $C_9$-알콜을 제조하는 공정에 사용하기 위한 최적의 촉매를 선정하고, $C_9$-알콜의 수율을 극대화하기 위한 운전 조건을 확립하기 위한 실험을 수행하였다. 구리 전구체로 acetate를 사용하고 침전제로 $Na_2CO_3$를 사용하여 제조한 $CuO/ZnO/Al_2O_3$(60:30:10 wt％) 촉매의 표면적 및 구리 비표면적이 가장 우수하였으며 $C_9$-알데히드 수소화 반응에서도 가장 우수한 성능을 보였다. 최적화된 촉매를 장착한 trickle bed 반응기를 사용하여 $175^{\circ}C$, 800 psi, $WHSV=3hr^{-1}$의 조건에서 94.1 wt％의 $C_9$-알콜 수율을 얻었다. 알데히드의 수소화 반응에 사용되는 다른 촉매들과 비교한 결과 Ni/kieselghur 촉매와 유사한 성능을 보였으며 $Cu-Ni-Cr-Na/Al_2O_3$ 촉매 및 $Ni-Mo/Al_2O_3$ 촉매의 경우보다 우수한 성능을 보이는 것을 확인하였다. 장기 촉매 테스트를 통해서 촉매의 안정성을 확인한 결과 약 72시간 이후에는 고비점 부산물의 생성량 증가로 인하여 $C_9$-알콜의 수율이 약간씩 감소하였다.