• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.563-568
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• 2005

The Pt/C and Pd/C catalysts were prepared from conventional chloride precursors by adsorption or precipitation-deposition methods. Their activities for hydrogenation reactions of cyclohexene and acetophenone were compared with those of commercial catalysts. The Pt/C and Pd/C catalysts obtained from the adsorption procedure reveal higher hydrogenation activity than commercial catalysts and the catalysts prepared by the precipitation-deposition method. Their improved performances are attributed to the decreased metal crystallite sizes of Pt or Pd formed on the active carbon support upon the adsorption of the precursors probably due to the same negative charges of the chloride precursor and the carbon support. Under the preparation conditions studied, the reduction of the supported catalysts using borohydrides in liquid phase is superior to a gas phase reduction by using hydrogen in the viewpoint of particle size, hydrogenation activity and convenience.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.141-146
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• 2014

A series of bimetallic Cu-Zn/$SiO_2$ catalysts were prepared via thermal decomposition of the as-synthesized $CuZn(OH)_4(H_2SiO_3)_2{\cdot}nH_2O$ hydroxides precursors. This highly dispersed Cu-solid base catalyst is extremely effective for hydrogenation of ethyl acetate to ethanol. The reduction and oxidation features of the precursors prepared by coprecipitation method and catalysts were extensively investigated by TGA, XRD, TPR and $N_2$-adsorption techniques. Catalytic activity by ethyl acetate hydrogenation of reaction temperatures between 120 and $300^{\circ}C$, different catalyst calcination and reduction temperatures, different Cu/Zn loadings have been examined extensively. The relation between the performance for hydrogenation of ethyl acetate and the structure of the Cu-solid base catalysts with Zn loading were discussed. The detected conversion of ethyl acetate reached 81.6% with a 93.8% selectivity of ethanol. This investigation of the Cu-Zn/$SiO_2$ catalyst provides a recently proposed pathway for ethyl acetate hydrogenation reaction to produce ethanol over Cu-solid base catalysts.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2034-2040
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• 2007

Efficient catalytic systems, where Ni or Pd is introduced in a supporting material of nanoporous carbon, have been developed for a liquid-phase hydrogenation of carboxylic acids and ketones at room temperature. It has been found that the catalysts reliably show high activities and selectivities for the hydrogenation to alcohols even in acidic conditions, and the catalytic activities depend on the preparative method of catalysts, the hydrogen pressure, the agitation rate, and the catalytic species. The hydrogenation of carboxylic acids and ketones clearly shows that the reaction rate is affected by the electronic and the steric effects, and a plausible reaction mechanism using metal hydrides as catalytic species is proposed.

• Bulletin of the Korean Chemical Society
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• 제29권12호
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• pp.2434-2440
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• 2008

The effect of sodium (Na) promotion was studied in the biphenol (BP) hydrogenation using various Pd/C catalysts. Different amounts of sodium metal were used for promotion with Pd/C and their effects on BP hydrogenation were observed. The promotion order was changed to compare the effect of the position of the promoter in relation to the palladium (Pd) metal on the catalytic activity and yield of the final product, bicyclohexyl-4,4'-diol (BHD). Pd/C catalysts prepared from different methods were also sodium-promoted and the changes of the reaction pathway according to the type of promoted Pd/C catalyst were compared.

• Bulletin of the Korean Chemical Society
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• 제29권2호
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• pp.328-334
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• 2008

The effects of catalyst preparation on the reaction route and the mechanism of biphenol (BP) hydrogenation, which consists of a long series-reaction, were studied. Pd/C catalysts were prepared by incipient wetness method and precipitation and deposition method. The reaction behaviors of the prepared catalysts and a commercial catalyst along with the final product distributions were very different. The choice of the catalyst preparation conditions during precipitation and deposition including the temperature, pH, precursor addition rate, and reducing agent also had significant effects. The reaction behaviors of the catalysts were interpreted in terms of catalyst particle size, metal distribution, and support acidities.

• 청정기술
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• 제28권4호
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• pp.331-338
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• 2022

본 연구의 목적은 열분해연료유(pyrolysis fuel oil, PFO)에 포함된 다환 방향족 탄화수소(polycyclic aromatic hydro, PAHs) 수소화 반응용 촉매로서 Pt(1wt%)/Kieselguhr 비드 촉매 및 펠렛 촉매를 제조하는 것이다. Trickle-bed 반응기에서 PFO-cut 수소화 반응을 통한 포화 고리 화합물(saturated cyclic compound)의 수율을 최대화하기 위한 최적의 반응 온도 및 수소/PFO-cut 유량비는 각각 250℃와 1800으로 결정하였다. PFO-cut의 공간속도(LHSV)가 감소할수록 포화 고리 화합물의 수율이 증가하였다. 펠렛 촉매와 비드 촉매의 수소화 반응 성능 차이는 크지 않았다. Kieselguhr 지지체를 성형한 후에 Pt를 담지한 촉매(AI 촉매)가 kieselguhr 분말에 Pt를 담지한 후에 성형한 촉매(BI 촉매)에 비해 수소화 활성이 높았으며, 이러한 경향은 펠릿 촉매와 비드 촉매에서 공통적으로 나타났다. 이는 AI 촉매의 Pt 활성점 수가 BI 촉매 보다 많기 때문이다. 본 연구에서 제조한 촉매 중에서 AI법으로 제조된 펠렛 촉매가 제조된 촉매 중 반응 활성이 가장 우수한 것을 확인하였다. PFO-cut 수소화 반응 생성물 중 C₈~C₁₅ 범위의 고리 화합물이 대부분을 차지했으며, C11 고리 화합물의 분포도가 가장 높았다. 수소화 반응과 더불어서 분해 반응도 함께 촉진되어 생성물의 탄소수 분포가 경질 탄화수소 쪽으로 이동함을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2726-2732
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• 2014

The promoting effect of rhodium on the structure and activity of the supported Cu-Co based catalysts for CO hydrogenation was investigated in detail. The samples were characterized by DRIFTS, $N_2$-adsorption, XRD, $H_2$-TPR, $H_2$-TPD and XPS. The results indicated that the introduction of rhodium to Cu-Co catalysts resulted in modification of metal dispersion, reducibility and crystal structure. DRIFTS results of CO hydrogenation at reaction condition (P=2 MPa, $T=260^{\circ}C$) indicated the addition of 1 wt % rhodium improved hydrogenation ability of Cu-Co catalysts. The ethanol selectivity and CO conversion were both improved by 1 wt % Rh promoted Cu-Co based catalysts. The alcohol distribution over un-promoted and rhodium promoted Cu-Co based catalysts obeys A-S-F rule and higher chain growth probability was got on rhodium promoted catalyst.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1512-1514
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• 2005

Catalytic properties of Ni-Zr$O_2$ catalysts prepared by coprecipitation have been studied for the gas-phase hydrogenation of 1,3-butadiene to butenes. The coprecipitation method led to the solid solution of Ni-Zr$O_2$, which contains highly resistant Ni species to thermal reduction with H2. Nickel species of the solid solution were highly dispersed in the ZrO2 lattice, so that the reduced catalysts were selective for hydrogenation of 1,3-butadiene to butenes (99.9%) even in the presence of 1-butene.

• 대한화학회지
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• 제40권6호
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• pp.445-452
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• 1996

Hydridonitrosyl complex의 촉매 활용 가능성과 반응 mechanism을 조사하기 위하여 $RuH(NO)(PPh_3)_3$와 RuH(NO)(etp)에 의한 ketone과 aldehyde의 수소화 반응을 연구하였다. 이 촉매들은 ketone과 aldehyde의 수소화 반응에 대하여 촉매 활성을 보이고 있으며, 활성은 기질의 입체장애 및 전자적 요인에 의존하고 있다. 즉, 입체 장애가 적을수록 촉매의 활성이 증가하며, 전자적 요인의 효과는 ketone의 경우 carbonyl carbon의 부분양전하의 양이 증가할수록, aldehyde의 경우는 carbonyl group의 double bond character가 강할수록 반응성이 증대되는 방향으로 나타나고 있다. 이러한 결과는 ketone과 aldehyde의 반응 mechanism이 다름을 반영하고 있다. 한편, RuH(NO)(etp)와 과잉의 $PPh_3$ 존재하에서 $RuH(NO)(PPh_3)_3$가 촉매 활성을 보이고 있음은 NO ligand의 결합방식의 변화를 통한 반응경로가 존재함을 확인하고 있다. 과잉의 $PPh_3$는 촉매와의 몰비가 변함에 따라 작용의 변화(ligand의 해리 방지 ${\rightarrow}$ 염기 ${\rightarrow}$ ligand)가 나타나며 촉매 활성에 영향을 미치고 있다. 이러한 결과를 이해하기 위하여 각 촉매에 대한 반응 mechanism을 제시하였다. 한편, 동일한 기질에 있어서 RuH(NO)(etp)의 활성은 항상 $RuH(NO)(PPh_3)_3$에 비하여 낮았으며 이는 주로 착물의 구조차이에 기인한 것으로 해석되며, 경쟁반응에 있어서는 olefin의 수소화 반응이 carbonyl group의 수소화 반응보다 선택적으로 진행되고 있다.

• 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.