• 자원리싸이클링
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• 제21권3호
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• pp.15-20
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• 2012

본 논문에서는 연료전지 막전극접합체에서 막분리 및 염산침출법을 이용하여 백금과 루테늄을 침출하는 연구를 하였다. 증류수, 10 vol.% 부탄올 용액, 15 vol.% 양이온 계면활성제(Koremul-LN-7)를 이용하여 연료전지 막전극접합체의 전해질막과 확산층을 침지법으로 촉매입자의 분산 없이 분리하였다. 그리고 질산 또는 과산화수소를 산화제로 하고 사용하는 염산에 의해 분리된 가스확산층의 촉매에 함유된 백금과 루테늄 금속을 침출하는 연구를 하였다. 과산화수소를 산화제로 사용하였을 때 백금과 루테늄의 침출율이 더 높았으며 최적 조건은 $90^{\circ}C$에서 염산 농도 8 M, 과산화수소 첨가량 5 M, 침출시간 6시간이었다. 이 조건에서 백금의 침출률은 98%, 루테늄의 침출율은 71.5%였다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.78-78
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• 2013

Recently, many platinoid metals like platinum and ruthenium have been used as an electrode of microelectronic devices because of their low resistivity and high work-function. However the material cost of Ru is very expensive and it usually takes long initial nucleation time on SiO2 during chemical deposition. Therefore many researchers have focused on how to enhance the initial growth rate on SiO2 surface. There are two methods to deposit Ru film with atomic layer deposition (ALD); the one is thermal ALD using dilute oxygen gas as a reactant, and the other is plasma enhanced ALD (PEALD) using NH3 plasma as a reactant. Generally, the film roughness of Ru film deposited by PEALD is smoother than that deposited by thermal ALD. However, the plasma is not favorable in the application of high aspect ratio structure. In this study, we used a bis(ethylcyclopentadienyl)ruthenium [Ru(EtCp)2] as a metal organic precursor for both thermal and plasma enhanced ALDs. In order to reduce initial nucleation time, we use several methods such as Ar plasma pre-treatment for PEALD and usage of sacrificial RuO2 under layer for thermal ALD. In case of PEALD, some of surface hydroxyls were removed from SiO2 substrate during the Ar plasma treatment. And relatively high surface nitrogen concentration after first NH3 plasma exposure step in ALD process was observed with in-situ Auger electron spectroscopy (AES). This means that surface amine filled the hydroxyl removed sites by the NH3 plasma. Surface amine played a role as a reduction site but not a nucleation site. Therefore, the precursor reduction was enhanced but the adhesion property was degraded. In case of thermal ALD, a Ru film was deposited from Ru precursors on the surface of RuO2 and the RuO2 film was reduced from RuO2/SiO2 interface to Ru during the deposition. The reduction process was controlled by oxygen partial pressure in ambient. Under high oxygen partial pressure, RuO2 was deposited on RuO2/SiO2, and under medium oxygen partial pressure, RuO2 was partially reduced and oxygen concentration in RuO2 film was decreased. Under low oxygen partial pressure, finally RuO2 was disappeared and about 3% of oxygen was remained. Usually rough surface was observed with longer initial nucleation time. However, the Ru deposited with reduction of RuO2 exhibits smooth surface and was deposited quickly because the sacrificial RuO2 has no initial nucleation time on SiO2 and played a role as a buffer layer between Ru and SiO2.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3331-3337
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• 2012

Ru-modified Pt nanoparticles of various sizes on platelet carbon nanofiber toward methanol oxidation were investigated in terms of particle size effect. The sizes of Pt nanoparticles, prepared by polyol method, were in the range of 1.5-7.5 nm and Ru was spontaneously deposited by contacting Pt nanoparticles with the Ru precursor solutions of 2 and 5 mM. The Ru-modified Pt nanoparticles were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The methanol oxidation activities of Ru-modified Pt nanoparticles, measured using cyclic voltammetry and chronoamperometry, revealed that when the Pt particle size was less than 4.3 nm, the mass specific activity was fairly constant with an enhancement factor of more than 2 at 0.4 V. However, the surface area specific activity was maximized on Pt nanoparticles of 4.3 nm modified with 5 mM Ru precursor solution. The observations were discussed in terms of the enhancement of poison oxidation by Ru and the population variation of Pt atoms at vertices and edges of Pt nanoparticles due to selective deposition of Ru on the facets of (111) and (100).

• Carbon letters
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• 제20권
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• pp.47-52
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• 2016

Physical and electrochemical qualities were analyzed after KOH activation of a direct methanol fuel cell using needle coke as anode supporter. The results of research on support loaded with platinum-ruthenium suggest that an activated KOH needle coke container has the lowest onset potential and the highest degree of catalyst activity among all commercial catalysts. Through an analysis of the CO stripping voltammetry, we found that KOH activated catalysis showed a 21% higher electrochemical active surface area (ECSA), with a value of 31.37 m² /g, than the ECSA of deactivated catalyst (25.82 m² /g). The latter figure was 15% higher than the value of one specific commercial catalyst (TEC86E86).

• 전기화학회지
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• 제5권4호
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• pp.221-225
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• 2002

Assisted by the highly sensitive confocal microprobe Raman spectrometer and proper surface roughening procedure, the Raman investigation on the adsorption and reaction of methanol was performed on Pt-Ru electrodes with different coverages. A detailed description of the roughening process of the Pt electrodes and the underpotential deposition of the Ru was given. Reasonably good Raman signal reflecting the metal-carbon vibration and CO vibration was detected. The appearance of vibrations of the Ru oxides, together with the existence of Ru-C, Pt-C and CO bands, clearly demonstrates the participation of the bi-functional mechanism during the oxidation process of methanol on Pt-Ru electrodes. The Pt-Ru electrode was found to have a higher catalytic activity over Pt electrodes. This preliminary study shows that electrochemical Raman spectroscopy can be applied to the study of rough electrode surface.

• 대한화학회지
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• 제57권6호
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• pp.726-730
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• 2013

Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong ${\sigma}$-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, $^1HNMR$, $^{31}PNMR$ and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

• 분석과학
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• 제10권4호
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• pp.264-273
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• 1997

수용액 중의 trihalomethane을 제거하기 위하여 양극 산화반응을 시키고 solid phase microextraction(SPME) fiber로 추출한 다음 GC-ECD로 분석하였다. 반응 용기 내부로 염소이온 등이 오염되는 것을 방지하기 위해 음극과 양극은 $KNO_3$-agar bridge로서 연결시켰다. 6종의 trihalomethane들은 성분에 따라 감도의 차이가 있었지만, 검량선은 수 ppb에서 수백 ppb 범위에서 좋은 직선관계를 보였다. 백금(Pt), 티탄(Ti), 지르코늄(Zr), Ti 금속상에 이리듐(Ir)을 도포시킨 고체 전극, 및 유리질 탄소에 루테늄(Ru)을 도포한 양극들을 사용하여 THM 성분을 제거하려 하였다. 제거효율이 가장 우수한 것은 Ti-Ir 양극으로서, 9V의 전압을 걸었을 때 약 1.5시간 이후에는 모든 성분들이 제거되었음을 알 수 있었다. 다양한 산화상태(mv)의 루테늄으로 유리질 탄소전극을 도포시킨 전극은 초기에는 제거효율이 우수하였으나, 시간이 경과할수록 전극 표면의 훼손으로 인해 제거효율은 약 60% 정도로 감소하였다. 특히 클로로포름은 약간 증가되는 경향을 보임으로써, 이것은 전극반응에 의하여 오히려 재생되는 것으로 생각된다.

• 전기화학회지
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• 제15권1호
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• pp.12-18
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• 2012

다양한 응용분야에서 활용될 수 있는 고체고분자연료전지의 경우 현재 상용화에 가장 큰 걸림돌이 되고 있는 것이 고가의 백금 촉매이다. 따라서 특히 최근 들어 산소환원반응에서 백금을 대체하는 물질을 개발하기 위한 연구가 전세계적으로 확산되고 있다. 그러나 촉매 개발 시 경제성 관점 외에 내구성도 고려해야 하는데, 이런 관점에서 백금과 유사한 물성과 활성이 기대되는 백금족 원소들이 한 대안이 될 것이다. 가장 백금과 유사한 물성, 활성을 나타내는 팔라듐과 칼코겐화물 형태의 루테늄이 지금까지 가장 많이 연구가 되었으며 상대적으로 이리듐, 로듐, 오스뮴은 산소환원 촉매로 많은 연구가 되지 않았다. RDE (rotating disk electrode)를 이용한 반쪽전지 실험이나 연료전지 MEA (membrane electrode assembly) 운전을 통하여 백금과 활성을 비교해보면 팔라듐 계열의 비백금 촉매가 가장 백금에 가까운 활성을 나타내고 있음을 알 수 있다. 이 논문에서는 각 백금족 원소들 기반의, 현재까지 문헌상으로 보고된 촉매조성들을 분석하여 비백금 산소환원 촉매 개발에 도움이 되고자 한다.

• 한국세라믹학회지
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• 제51권4호
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• pp.362-366
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• 2014

Dye-sensitized solar cells (DSSCs) were synthesized using a $0.25cm^2$ area of a $TiO_2$ nanoparticle layer as the electrode and platinum (Pt) as the counter electrode. The $TiO_2$ nanoparticle layers (12 to 22 ${\mu}m$) were screen-printed on fluorine-doped tin oxide glass. Glancing angle X-ray diffraction results indicated that the $TiO_2$ layer is composed of pure anatase with no traces of rutile $TiO_2$. The Pt counter electrode and the ruthenium dye anchored $TiO_2$ electrode were then assembled. The best photovoltaic performance of DSSC, which consists of a $18{\mu}m$ thick $TiO_2$ nanoparticle layer, was observed at a short circuit current density ($J_{sc}$) of $14.68mA{\cdot}cm^{-2}$, an open circuit voltage ($V_{oc}$) of 0.72V, a fill factor (FF) of 63.0%, and an energy conversion efficiency (${\eta}$) of 6.65%. It can be concluded that the electrode thickness is attributed to the energy conversion efficiency of DSSCs.

• Journal of Electrochemical Science and Technology
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• 제1권1호
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• pp.19-24
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• 2010

Alloying degree is an important structural factor of PtRu catalysts for direct methanol fuel cells (DMFC). In this work, carbon supported PtRu catalysts were synthesized by reduction method using anhydrous ethanol as a solvent and $NaBH_4$ as a reducing agent. Using anhydrous ethanol as a solvent resulted in high alloying degree and good dispersion. The morphological structure and crystallanity of synthesized catalysts were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM). CO stripping and methanol oxidation reaction were measured. Due to high alloying degree catalyst prepared in anhydrous ethanol, exhibited low onset potential for methanol oxidation and negative peak shift of CO oxidation than commercial sample. Consequently, samples, applying ethanol as a solvent, exhibited not only enhanced CO oxidation, but also increased methanol oxidation reaction (MOR) activity compared with commercial PtRu/C (40 wt%, E-tek) and 40 wt% PtRu/C prepared in water solution.