• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.212-212
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• 2011

In addition to the catalysts' activity and selectivity, the deactivation of catalysts during use is of practical importance. It is crucial to understand the phenomena of the deactivation to predict the loss of activity during catalyst usage so that the high operational costs associated with catalyst replacement can be reduced. In this study, the activity of Ru catalysts, such as nanoparticles (3~6 nm) and polycrystalline thin film (50 nm), have been investigated under CO oxidation and oxidative/reductive reaction conditions at various temperatures with the ambient pressure X-Ray photoelectron spectroscopy (APXPS). With APXPS, the surface oxides on the catalyst are measured and monitored in-situ. It was found that the Ru film exhibited faster oxidation-and-reduction compared to that of nanoparticles showing mild oxidative-and-reductive characteristics. Additionally, the larger Ru nanoparticles showed a higher degree of oxide formation at all temperatures, suggesting a higher stability of the oxide. These observations are in agreement with the catalytic activity of Ru catalysts. The loss of activity of Ru films is correlated with bulk oxide formation, which is inactive in CO oxidation. The Ru nanoparticle, however, does not exhibit deactivation under similar conditions, suggesting that its surface is covered with a highly active ultrathin surface oxide. Since the active oxide is more stable as nanoparticles than as a film, the nanoparticles showed mild oxidative/reductive behavior, as confirmed by APXPS results. We believe these simultaneous observations of both the surface oxide of Ru catalysts and the reactivity in real time enable us to pinpoint the deactivation phenomena more precisely and help in designing more efficient and stable catalytic systems.

• Journal of Electrochemical Science and Technology
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• 제10권3호
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• pp.271-275
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• 2019

Anodic $TiO_2$ nanotubes were simultaneously grown and doped with $RuO_2$ by single-step anodization in a negatively-charged $RuO_4{^-}$ precursor. Subsequently, a high positive voltage was imposed on the nanotubes in an $F^-$-based electrolyte (a process referred to as potential shock), which led to the formation of a through-hole $RuO_2$-doped $TiO_2$ nanotube membrane without significant loss of the $RuO_2$ catalyst. XPS results confirmed that the doped Ru metal was converted into $RuO_2$ as the potential shock voltage increased. Further increases in the potential shock voltage led to the formation of $RuO_x/Ru$ in the $TiO_2$ nanotubes. All of our results clearly showed that a through-hole catalyst-doped $TiO_2$ nanotube membrane can be produced by a sequence consisting of single-step anodization and the potential shock process.

• Korean Chemical Engineering Research
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• 제46권3호
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• pp.581-584
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• 2008

중기공성 층상화합물의 촉매 담체를 제조하고, 메탄으로부터 수소를 제조하기 위한 활성도를 평가하기 위해서 고정층 상압 유통식 반응기를 사용하여 Ru(3)/SPK와 Ru(3)/SPM 촉매상에서 메탄의 부분산화반응를 수행하였다. 또한, BET, TEM, TPR를 사용하여 촉매 및 담체의 특성을 분석하였다. 촉매 담체인 실리카 지주 $H^+-kenyaite$(SPK) 와 $H^+-magadite$(SPM)의 BET 비 표면적은 각각 $760m^2/g$와 $810m^2/g$ 이었고, 평균기공크기는 각각 3.0 nm와 2.6 nm 이었다. $N_2$-흡착등온선은 히스테리시스가 잘 발달된 IV형이었으며, TEM으로 중기공성 층상화합물이 잘 만들어졌음을 확인할 수 있었다. Ru(3)/SPK와 Ru(3)/SPM 촉매는 973 K, $CH_4/O_2=2$, $1.25{\times}10^{-5}g-Cat.hr/ml$의 반응조건에서 각각 90%, 87%의 수소의 수율를 얻을 수 있었으며, 약 60시간 까지도 높은 수소 수율을 유지하였다. Ru(3)/SPK와 Ru(3)/SPM 촉매의 TPR 피크는 각각 453K와 413K의 근방에서 비슷한 환원도를 보여주었다. 이러한 분석자료로부터 SPK와 SPM은 산화반응의 촉매 담체로서 구비조건(비 표면적, 열안정성, 평균기공크기 등)를 갖추고 있음을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제19권6호
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• pp.467-473
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• 2008

This study is to investigate the influence of catalyst loading quantity on the direct methanol fuel cell (DMFC) performance. In this paper, Pt-Ru and Pt-black loading as the catalyst were varied from 1 to $4mg/cm^2$ at the anode and cathode, respectively. The experiment was conducted with single fuel cell consisted of $5cm^2$ effective electrode area, serpentine type flow pattern and Nafion 117 membrane. Also, AC impedance and methanol crossover current were measured to investigate the performance loss precisely. As a result, the performance of fuel cell was significantly increased with the increase of cathode catalyst loading. However, the performance did not increase further above a certain Pt-Ru catalyst loading as the increase of anode catalyst loading.

• Carbon letters
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• 제11권4호
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• pp.336-342
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• 2010

Different oxidation treatments on CNTs using diluted 4.0 M $H_2SO_4$ solution at room temperature and or at $90^{\circ}C$ reflux conditions were investigated to elucidate the physical and chemical changes occurring on the treated CNTs, which might have significant effects on their performance as catalyst supports in PEM fuel cells. Raman spectroscopy, X-ray diffraction and transmission electron microscope analyses were made for the acid treated CNTs to determine the particle size and distribution of the CNT-supported Pt-Ru nanoparticles. These CNT-supported Pt-based nanoparticles were then employed as anode catalysts in PEMFC to investigate their catalytic activity and single-cell performance towards $H_2$ oxidation. Based on PEMFC performance results, refluxed Pt-Ru/CNT catalysts prepared using CNTs treated at $90^{\circ}C$ for 0.5 h as anode have shown better catalytic activity and PEMFC polarization performance than those of the commercially available Pt-Ru/C catalyst from ETEK and other Pt-Ru/CNT catalysts developed using raw CNT, thus demonstrating the importance of acid treatment in improving and optimizing the surface properties of catalyst support.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3576-3582
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• 2014

Zeolite-templated carbons (ZTCs), which have high specific surface area, were prepared by a conventional templating method using microporous zeolite-Y for catalyst supports in direct methanol fuel cells. The ZTCs were synthesized at different temperatures to investigate the characteristics of the surface produced and their electrochemical properties. Thereafter, Pt-Ru was deposited at different carbonization temperatures by a chemical reduction method. The crystalline and structural features were investigated using X-ray diffraction and scanning electron microscopy. The textural properties of the ZTCs were investigated by analyzing $N_2$/77 K adsorption isotherms using the Brunauer-Emmett-Teller equation, while the micro- and meso-pore size distributions were analyzed using the Barrett-Joyner-Halenda and Harvarth-Kawazoe methods, respectively. The surface morphology was characterized using transmission electron microscopy and inductively coupled plasma-mass spectrometry. The electrochemical properties of the Pt-Ru/ZTCs catalysts were also analyzed by cyclic voltammetry measurements. From the results, the ZTCs carbonized at $900^{\circ}C$ show the highest specific surface areas. In addition, ZTC900-PR led to uniform dispersion of Pt-Ru on the ZTCs, which enhanced the electro-catalytic activity of the Pt-Ru catalysts. The particle size of ZTC900-PR catalyst is about 3.4 nm, also peak current density from the CV plot is $12.5mA/cm^2$. Therefore, electro-catalytic activity of the ZTC900-PR catalyst is higher than those of ZTC1000-PR catalyst.

• 공업화학
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• 제35권2호
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• pp.134-139
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• 2024

메탄의 수증기 개질 반응에서 Ni 기반 촉매에 귀금속 Ru 및 Pd을 조촉매로 첨가하여 촉매의 활성 및 수소 생산에 미치는 영향을 분석하였다. 합성된 촉매는 허니컴 구조의 금속 모노리스 구조체 표면에 코팅하여 수증기 메탄 개질 반응을 수행하였다. 촉매의 특성은 XRD, TPR 및 SEM으로 분석하였으며 개질 반응 후 가스를 포집하여 GC로 조성을 분석한 후 메탄의 전환율, 수소 수율 및 CO 선택도를 측정하였다. 0.5 wt%의 Ru 첨가는 Ni의 환원 특성을 개선하였고, 99.91%의 메탄 전환율로 향상된 촉매 활성을 나타내었다. 또한, 다양한 공정 조건에 따른 반응 특성을 분석하였으며, 800 ℃의 반응 온도, 10000 h^-1 이하의 공간속도(GHSV), 3 이상의 H₂O와 CH₄의 비(S/C)에서 90% 이상의 메탄 전환율과 3.3 이상의 수소 수율을 얻을 수 있었다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 추계학술대회 초록집
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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.

• Carbon letters
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• 제4권3호
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• pp.121-125
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• 2003

The Pt-Ru/Carbon as an anode catalyst supported on the commercial activated carbon (AC) having high surface area and micropore was characterized for application of Direct Methanol Fuel Cell (DMFC). The Pt-Ru/AC anode catalyst used in this experiment showed the performance of $600\;mA/cm^2$ current density at 0.3 V. The borohydride reduction process using $NaBH_4$, denoted as a process A, showed much higher current and power densities than process B prepared by changing the reduction and washing process of process A. The particle sizes are strongly affected by the reduction process than the specific surface area of raw active carbon and the sizes are almost constant when the specific surface area of carbon are over than the $1200\;m^2/g$. Smaller particle size of catalyst and more narrow intercrystalite distance increased the performance of DMFC.

• 공업화학
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• 제25권6호
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• pp.645-647
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• 2014

본 연구에서는 수열합성법을 이용하여, 한단계의 과정으로 $TiO_2$와 Ru (Ruthenium)가 도입된 $TiO_2$ ($Ru_x/TiO_2$)를 합성하였다. 합성된 샘플의 결정성과 조성 및 형태를 X-ray diffraction (XRD)과 energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM)를 통하여 확인하였으며, Benzyl alcohol의 Benzaldehyde로의 산화반응에 촉매로서 적용하였다. 높은 선택성을 가지는 산화반응이 진행되었으며, $TiO_2$에 도입된 Ru의 양이 증가할수록 촉매로서의 더 좋은 촉매활성을 보였다.