• 공업화학
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• 제7권4호
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• pp.661-669
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• 1996

NaY 제올라이트에 Pt/Rh비를 달리하여 이온교환법으로 제조한 Pt-Rh촉매의 특성을$^{129}Xe$-NMR과 EXAFS 방법으로 특성조사를 하였다. $^{129}Xe$-NMR과 EXAFS 자료는 PtRh 이원금속 클러스터의 표면으로 Rh 원자들이 모이는 것으로 나타났다. 모사 자동차 배기가스를 사용하여 희박, 과농 및 양론조건에서 CO, HC 및 $NO_x$ 전환율을 측정하였으며, Pt-Rh/NaY(Pt/Rh=1) 이원금속 촉매가 다른 촉매들보다 세가지 오염물질에 대한 반응활성이 높게 나타남을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제23권4호
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• pp.563-566
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• 2002

Copper complexes have been directly incorporated into cellulose acetate (CA) and the resulting light blue colored homogeneous films of 5-20 wt.% copper acetate complex concentrations are found to be thermally stable up to 200 $^{\circ}C$. The reaction chem istry of Cu in CA has been investigated by reacting them with small gas molecules such as CO, H2, D2, O2, NO, and olefins in the temperature range of 25-160 $^{\circ}C$, and various Cu-hydride, -carbonyl, -nitrosyl, and olefin species coordinated to Cu sites in CA are characterized by IR and UV/Vis spectroscopic study. The reduction of Cu(II) complexes by reacting with H2 gas at the described conditions results in the formation of Cu2O and copper metal nanoparticles in CA, and their sizes in 30-120 nm range are found to be controlled by adjusting metal complex concentration in CA and/or the reduction reaction conditions. These small copper metal particles show various catalytic reactivity in hydrogenation of olefins and CH3CN; CO oxidation; and NO reduction reactions under relatively mild conditions.

• Bulletin of the Korean Chemical Society
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• 제28권1호
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• pp.17-28
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• 2007

Indium and gallium have emerged as useful metals in organic synthesis as a result of its intriguing chemical properties of reactivity, selectivity, and low toxicity. Although indium belongs to a main metal in group 13, its first ionization potential energy is very low and stable in H2O and O2. Therefore, indium-mediated organic reactions are of our current interest. On the basis of these properties of indium, many efficient indium-mediated organic reactions have been recently developed, such as the addition reactions of allylindium to carbonyl and iminium groups, the indium-mediated synthesis of 2-(2-hydroxyethyl)homoallenylsilanes, the indiummediated allylation of keto esters with allyl halides, sonochemical Reformatsky reaction using indium, the indium-mediated selective introduction of allenyl and propargyl groups at C-4 position of 2-azetidinones, the indium-mediated Michael addition and Hosomi-Sakurai reactions, the indium-mediated β-allylation, β- propargylation and β-allenylation onto α,β-unsaturated ketones, the highly efficient 1,4-addition of 1,3-diesters to conjugated enones by indium and TMSCl, and the intramolecular carboindation reactions. Also, we found gallium-mediated organic reactions such as addition reactions of propargylgallium to carbonyl group and regioselective allylgallation of terminal alkynes.

• 한국수소및신에너지학회논문집
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• 제30권1호
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• pp.1-7
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• 2019

The preparation and catalytic activities of various transition metal carbide crystallites (VC, MoC, WC) were examined in this study. In particular, the effect of different kinds of transition metal crystallites were scrutinized on the ammonia decomposition reaction. The experimental results showed that BET surface areas ranged from $8.3m^2/g$ to $36.3m^2/g$ and oxygen uptake values varied from $9.1{\mu}mol/g$ to $25.4{\mu}mol/g$. Amongst prepared transition metal carbide crystallites, tungsten compounds (WC) were observed to be most active for ammonia decomposition reaction. The main reason for these results were considered to be related to the extent of electronegativity between these materials. Most of transition metal carbide crystallites were exceeded by Pt/C crystallite. However, the steady state reactivities for some of transition metal carbide crystallites (WC) were comparable to or even higher than that determined for the Pt/C crystallite.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

• 에너지공학
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• 제23권3호
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• pp.150-156
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• 2014

본 연구는 바나듐 레독스 흐름전지에서 속도 결정단계인 양극 반응($[VO]^{2+}/[VO_2]^+$)을 개선하여 바나듐 반응의 속도를 증가시켜 흐름전지 성능을 향상시키고자 하는 목적으로 진행하엿다. 이를 위해, 다공성 촉매인 CMK3를 사용하여 일반적으로 사용되는 탄소 (Vulcan(XC-72)) 및 상용 Pt/C 촉매 (Johnson-Matthey사 Pt 20wt.%)와 그 성능을 비교하였다. 반응성은 순환주사전류법으로, 구조적 특성은 TEM과 BET&BJH을 이용하여 분석하였다. 또한, 완전지 실험을 통하여 전기화학적으로 나타난 결과가 어떻게 충방전에 적용되는지 확인하였다. 결과, CMK3는 Vulcan(XC-72)보다 6배 향상된 촉매 활성과 2배 이상 향상된 반응가역성이 나타남을 확인하였고, CMK3의 다공성 구조로 인해 Vulcan(XC-72) 보다 큰 표면적을 가지고 있음을 확인하였다. 아울러, CMK3는 백금 촉매가 없음에도, 상용 Pt/C 촉매의 85% 이상의 반응성과 가역성을 나타내었다. 완전지 실험에서 충방전 곡선은 CMK3를 적용한 흐름전지가 오히려 상용 Pt/C 촉매를 적용한 흐름전지보다 좋은 모습을 나타내었다.

• 공업화학
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• 제9권1호
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• pp.141-148
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• 1998

초강산 담체인 $ZrO_2$ $SO_4{^{2-}}$에 담지된 백금촉매(0.2, 0.5wt% Pt)의 저온 산화반응성을 cyclohexane의 완전산화반응에 대하여 조사 하였다. 충전층 관형반응기에서 반응물질의 전화율로 측정된 촉매활성은 촉매의 산성도와 비표면적에 비례하여 증가하였다 : $Pt/ZrO_2$ $SO_4{^{2-}}$ 촉매 제조과정에서 K(potassium)를 첨가하여 촉매의 산성도와 비표면적을 감소시켰을 때 촉매활성은 K첨가량에 비례하여 감소하였다. 또한 $Pt/ZrO_2$ $SO_4{^{2-}}$촉매는 훨씬 더 큰 비표면적을 가진 $Pt/SiO_2$, 또는 $Pt/Al_2O_3$촉매보다 뛰어난 활성을 보였다 : l5,000ppm cyclohexane농도와 $18,000hr^{-1}$공간속도를 가진 반응물질 흐름을 $250^{\circ}C$에서 0.2wt% $Pt/ZrO_2$ $SO_4{^{2-}}$촉매를 사용하여 전화시킨 결과 96%의 cyclohexane전화율을 보인 반면, 같은 반응조건 하에서 0.2wt% $Pt/SiO_2$와 0.2wt% $Pt/Al_2O_3$촉매는 각각 83%와 79%의 cyclohexane전화율을 보였다.

• 공업화학
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• 제17권3호
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• pp.235-242
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• 2006

Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.

• Korean Chemical Engineering Research
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• 제50권2호
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• pp.217-222
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• 2012

이산화탄소를 이용하여 디메틸카보네이트(DMC)를 제조하는 반응은 지구온난화 현상의 주요 원인으로 지적되는 이산화탄소의 효율적 전환 방법의 하나로 주목 받고 있다. DMC는 유독한 포스겐과 디메틸슬페이트를 대체하는 반응 매개체, 가솔린 연료 첨가제, 폴리카보네이트 수지의 전구체 등으로 다양하게 활용되고 있다. 본 연구에서는 에틸렌카보네이트(EC)와 메탄올의 에스테르 교환반응에 의한 DMC의 제조 반응에 대하여 이온성 액체와 금속 촉매의 특성을 조사하였다. 촉매 스크리닝 실험 결과 [Choline][OH]와 [BMIm][OH]가 금속염인 MgO, ZnO, CaO보다 더 좋은 촉매 활성을 나타내었다. [Choline][OH] 촉매에 대해서 반응변수인 반응온도, MeOH/EC 몰비, 이산화탄소 압력이 반응에 미치는 영향을 고찰하였다. 반응온도가 높고 MeOH/EC 몰비가 클수록 EC의 전화율이 증가하였다. 그러나 이산화탄소 압력의 영향에서는 1.34 MPa에서 최고의 DMC 수율을 나타내었고 그 이상의 압력에서는 DMC 수율이 오히려 감소하였다. $ZnCl_2$를 조촉매로 사용한 경우 각각 촉매의 활성보다 더 높은 활성을 나타내어 시너지 효과가 관찰되었으며, 이것은 혼합촉매의 산-염기적 특성에 기인하는 것으로 판단된다.

• Korean Chemical Engineering Research
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• 제53권5호
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• pp.653-662
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• 2015

일반적으로 가스화는 고온($1300{\sim}1400^{\circ}C$), 고압(30~40 bar)에서 공정이 가동되나 이를 유지하기 위해 과도한 에너지가 사용된다. 본 연구에서는 공정 온도를 줄이기 위해 알칼리 촉매 중 $K_2CO_3$과 $Na_2CO_3$을 저등급의 사이프러스(Cyprus) 탄에 첨가하였고, 이산화탄소 분위기에서 가스화시켰을 때 나타나는 반응특성을 연구하였다. 열중량분석기를 활용하여 촉매의 함량, 촉매의 종류, 온도를 변수로서 가스화 공정조건을 결정하였다. 고체상 물리적 혼합법으로 촉매를 도입 시, 7 wt%의 $Na_2CO_3$가 첨가된 시료가 원탄보다 높은 활성을 보였다. 탄소전환율 거동을 예측하기 위해 시료별로 반응모델을 적용해본 결과, volumetric reaction model(VRM)이 탄소전환율 거동을 가장 잘 묘사하였다. 7 wt%의 $Na_2CO_3$을 첨가한 사이프러스 탄의 활성화 에너지는 63 kJ/mol로 원탄보다 낮으며, 이는 이산화탄소 분위기에서 석탄가스화의 반응성을 향상시킨다는 것을 보여주었다.