• Clean Technology
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• v.29 no.2
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• pp.79-86
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• 2023

The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

• Transactions of the Korean hydrogen and new energy society
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• v.4 no.2
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• pp.5-15
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• 1993

Hydrogen production in visible light with the following semiconductor systems, $CdS-WO_3$, $CdS-TiO_2$, have been investigated in the presence of redox catalyst (Pt, $RuO_2$). MeOH, EtOH, isopropanol, sulfide/sulfite mixture, lactic acid were used as sacrifical reagents. The optimal condition for $H_2$ evolution was found to be in qgueous lactic acid media for $CdS-WO_3/RuO_2$. The photochemical efficiency for this system was 1.05 % and the $H_2$ evolution rate was 26.5ml/min. at $6.07{\times}10^{-5}$ einstein/sec photon rate

• Korean Journal of Metals and Materials
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• v.50 no.3
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• pp.243-247
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• 2012

A ruthenium (Ru) catalytic layer and a conventional Pt layer were assessed as counter electrodes (CE) for dye sensitized solar cells (DSSCs). Ru films with different thicknesses of 34, 46, and 90 nm were deposited by atomic layer deposition (ALD). Pt layers with the same thicknesses were prepared by sputtering. $0.45cm^2$ DSSCs were prepared and their properties were characterized by FE-SEM, cyclic voltammetry (CV), impedance spectroscopy (EIS), and current-voltage (I-V). FE-SEM revealed that the crystallized Ru films and Pt films had been deposited quite conformally. CV showed that the catalytic activity of Pt was much greater than that of Ru. In addition, although the catalytic activity of Pt did not depend on the thickness, that of Ru showed an increase with increasing thickness. Impedance analysis revealed high charge transfer resistance at the Ru interface and a decrease with increasing Ru thickness, whereas Pt showed low resistance with no thickness dependence. Despite the relatively small catalytic activity of Ru, the I-V result revealed the average energy conversion efficiency of Ru and Pt to be 2.98% and 6.57%, respectively. These results suggest that Ru can be used as counter electrodes in DSSCs due to its extremely low temperature process compatibility.

• Environmental Engineering Research
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• v.7 no.1
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• pp.11-19
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• 2002

• 한국전기화학회:학술대회논문집
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• 2001.06a
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• pp.167-170
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• 2001

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.652-655
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• 2009

The bimodal porous carbons were synthesized by using imprinting method with templates of SBA-15 particle and silica sphere and applied as supporting materials for the electro-catalyst of polymer electrolyte fuel cell (PEFC). The silica spheres with diameter size of 100 nm and SBA-15 particle having 200 nm -250 nm diameter and 700 nm -900 nm length were synthesized in this work. The bimodal porous carbons (S100) were prepared by using the silica spheres and SBA-15 as templates and mesophase pitch as a carbon source. The PtRu nanoparticle of ca. 1.9 nm were supported on the bimodal porous carbon support and the resulting PtRu/S100 catalysts was tested by the cyclic voltammetry. The use of bimodal porous carbon showed in comparable electro-catalytic activities with commercial catalyst. Though unclear effects of bimodal porosity of supports could be obtained in the scope of this study, morphological advantage in electrical conductivity can be considered on the electro-catalytic activity.

• Advances in Energy Research
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• v.2 no.1
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• pp.21-31
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• 2014

The use of a microporous membrane along with Au/C catalyst for direct glycerol alkaline fuel cell was investigated. In comparison with Nafion 112, the microporous Celgard 3401 membrane provides a better cell performance due to the lower ionic resistance as confirmed by impedance spectra. The single cell using Au/C as anode catalyst prepared by using PVA protection techniques provided a higher maximum power density than the single cell with commercial PtRu/C at $18.65mW\;cm^{-2}$ The short-term current decay studies show a better stability of Au/C single cell. The higher activity of Au/C over PtRu/C was owing to the lower activation loss of Awe. The magnitude of current decay indicates a low problem of glycerol crossover from anode to cathode side. The similar performance of single cell with and without humudification at cathode points out an adequate transport of water through the microporous membrane.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.97.2-97.2
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• 2011

Pt-Ru and Pt-Ni bimetallic catalysts were prepared and tested for heavy hydrocarbon reforming. Metals were supported on CGO($Ce_{0.8}Gd_{0.2}O_{2.0-x}$) by incipient wetness method. The prepared catalysts were characterized by Temperature programmed reduction(TPR). Oxidative steam reforming of n-dodecane was conducted to compare the activity of the catalysts. The reforming temperature was varied from $500^{\circ}C$ to $800^{\circ}C$ at fixed $O_2$/C of 0.3, $H_2O$/C of 3.0 and GHSV of 5,000/h.Reduction peaks of metal oxide, surface CGO and bulk CGO were detected. Reduction temperature of metal oxide decreased over the bi-metallic catalysts. It is considered that interaction between metals leads to decrease interaction between metal and oxygen. On the other hands, reduction temperatures of surface CGO were dectected in the order of Pt-Ru > Pt-Ni > Pt. low reduction temperatures of surface CGO indicates the low activation energy for oxygen ion conduction to metal. Oxygen ion conduction is known as de-coking mechanism of ionic conducting supports such as CGO. In activity test, fuel conversion was in the same order of Pt-Ru > Pt-Ni > Pt. Especially, 100% of fuel conversion was obtained over Pt-Ru catalysts at $500^{\circ}C$.

• Applied Chemistry for Engineering
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• v.23 no.6
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• pp.561-566
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• 2012

PtRuW/C catalysts were prepared with the different molar ratios of Pt : Ru : W and their compositions were analyzed by energy dispersive X-ray (EDX). The uniform distribution of particles was observed using transmission electron microscopy (TEM). An average crystalline size of 3.5~5.5 nm was calculated based on x-ray diffraction (XRD) data. The electrochemical properties such as electrochemically active surface areas, current densities, specific activities and poisoning rates, were analyzed via CO stripping, linear sweep voltammetry and chronoamperometry. From the analysis, we observed that ternary alloy catalysts, except $PtRu_2W_2/C$, have higher current densities, specific activities and stabilities than those of commercial binary catalysts. Among all in-house catalysts, Pt5Ru4W/C showed the highest specific activity of $121.05mA{\cdot}m^{-2}$ and the lowest poisoning rate of $0.01%{\cdot}s^{-1}$.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.228.1-228.1
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• 2010

선택적 CO 산화반응(PrOx)을 위한 Ru이 고분산 담지된 $Ru/{\alpha}-Al_2O_3$ 촉매를 증착-침전법(deposition-precipitation)으로 제조하였다. 용액의 pH와 aging 시간에 따른 Ru 입자의 크기 변화와 분산도의 영향을 살펴보았으며 함침법(impregnation)으로 비교 촉매를 제조하였다. 촉매의 특성분석은 BET, TPR, CO-Chemisorption분석을 수행하여 촉매의 비표면적, 환원특성, 분산도를 알 수 있었다. 특성분석결과, 증착-침전법으로 제조한 $Ru/{\alpha}-Al_2O_3$ 촉매가 함침법으로 제조한 촉매에 비해 분산도가 높았으며, pH별 촉매 제조에서는 pH6.5로 제조한 촉매가 22.06%로 가장 높은 분산도를 보였다. 또한, 담체의 비표면적 영향에 따른 Ru 입자의 분산도를 살펴보기 위해 ${\gamma}-Al_2O_3$와 ${\alpha}-Al_2O_3$ 담체를 적용한 결과, 비표면적이 작은 ${\alpha}-Al_2O_3$ 담체 표면에서 Ru 분산도가 ${\gamma}-Al_2O_3$ 담체에 비해 높았다. 이는 기공이 발달하여 비표면적이 넓은 ${\gamma}-Al_2O_3$ 담체는 소량의 Ru을 고분산 담지 시 담체 표면보다는 기공 내에 담지 되는 양이 많아 실제 반응 시 반응에 참여하는 표면 활성 금속양이 적음을 알 수 있다. 특히, 선택적 산화반응과 같이 표면에서 빠른 반응이 일어나는 경우, 기공 내부의 활성금속이 반응에 참여하기 어려워 반응 활성이 낮음을 PrOx 반응실험을 통해 확인할 수 있었다. PrOx test 조건은 GHSV 250000~60000, 온도는 80~200도, 람다값은 2~4로 성능 비교하여 실험 하였다. PrOx의 성능평가 결과 담체를 ${\alpha}-Al_2O_3$를 사용하여 deposition-precipitation방법으로 제조한 pH6.5 촉매에서 $100{\sim}160^{\circ}C$에서 90%의 가장 높은 CO conversion을 가지고 18%의 선택도를 가졌다.