• 한국재료학회지
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• 제21권8호
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• pp.419-424
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• 2011

Pt nanoparticle catalysts incorporated on $RuO_2$ nanowire support were successfully synthesized and their electrochemical properties, such as methanol electro-oxidation and electrochemically active surface (EAS) area, were demonstrated for direct methanol fuel cells (DMFCs). After fabricating $RuO_2$ nanowire support via an electrospinning method, two different types of incorporated Pt nanoparticle electrocatalysts were prepared using a precipitation method via the reaction with $NaBH_4$ as a reducing agent. One electrocatalyst was 20 wt% Pt/$RuO_2$, and the other was 40 wt% Pt/$RuO_2$. The structural and electrochemical properties of the Pt nanoparticle electrocatalysts incorporated on electrospun $RuO_2$ nanowire support were investigated using a bright field transmission electron microscopy (bright field TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. The bright field TEM, XRD, and XPS results indicate that Pt nanoparticle electrocatalysts with sizes of approximately 2-4 nm were well incorporated on the electrospun $RuO_2$ nanowire support with a diameter of approximately 50 nm. The cyclic voltammetry results showed that the Pt nanoparticle catalysts incorporated on the electrospun $RuO_2$ nanowire support give superior catalytic activity in the methanol electro-oxidation and a higher electrochemically active surface (EAS) area when compared with the electrospun Pt nanowire electrocatalysts without the $RuO_2$ nanowire support. Therefore, the Pt nanoparticle catalysts incorporated on the electrospun $RuO_2$ nanowire support could be a promising electrode for direct methanol fuel cells (DMFCs).

• 대한화학회지
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• 제64권1호
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• pp.49-53
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• 2020

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 춘계학술대회 초록집
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• pp.93.2-93.2
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• 2011

In this work, graphite nanofibers (GNFs) were prepared for using catalyst supports in fuel cells. The GNFs were chemically activated to obtain high surface area and small pore diameter with different potassium hydroxide (KOH) amounts, i.e., 0, 1, 3, 4, and 5 g as an activating agent. And then Pt-Ru was deposited onto activated GNFs (A-GNFs) by chemical reduction method. The characteristics of Pt-Ru catalysts deposited onto A-GNFs were determined by specific surface area and pore size analyzer, X-ray diffraction (XRD), transmission electron microscopy (TEM), and inductive coupled plasma-mass spectrometer (ICP-MS). The electrochemical properties of Pt-Ru/A-GNFs catalysts were also analyzed by cyclic voltammetry (CV) experiments. From the results, the A-GNFs carbon supports activated with 4 g of KOH (A4g-GNFs) showed that the highest specific surface areas. In addition, the A4g-GNFs led to uniform dispersion of Pt-Ru onto A4g-GNFs, resulting in the enhancement of electrochemical activity of Pt-Ru catalysts.

• 한국재료학회지
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• 제28권6호
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• pp.365-369
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• 2018

We perform density functional theory calculations to study the CO and $O_2$ adsorption chemistry of Pt@X core@shell bimetallic nanoparticles (X = Pd, Rh, Ru, Au, or Ag). To prevent CO-poisoning of Pt nanoparticles, we introduce a Pt@X core-shell nanoparticle model that is composed of exposed surface sites of Pt and facets of X alloying element. We find that Pt@Pd, Pt@Rh, Pt@Ru, and Pt@Ag nanoparticles spatially bind CO and $O_2$, separately, on Pt and X, respectively. Particularly, Pt@Ag nanoparticles show the most well-balanced CO and $O_2$ binding energy values, which are required for facile CO oxidation. On the other hand, the $O_2$ binding energies of Pt@Pd, Pt@Ru, and Pt@Rh nanoparticles are too strong to catalyze further CO oxidation because of the strong oxygen affinity of Pd, Ru, and Rh. The Au shell of Pt@Au nanoparticles preferentially bond CO rather than $O_2$. From a catalysis design perspective, we believe that Pt@Ag is a better-performing Pt-based CO-tolerant CO oxidation catalyst.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.133-133
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• 2013

For both oxygen reduction (ORR) and hydrogen oxidation reactions (HOR) of proton electrolyte membrane fuel cells (PEMFCs), alloying Pt with another transition metal usually results in a higher activity relative to pure Pt, mainly due to electronic modification of Pt and bifunctional behaviour of alloy surface for ORR and HOR, respectively. However, activity and stability are closely related to the preparation of alloy nanoparticles. Preparation conditions of alloy nanoparticles have strong influence on surface composition, oxidation state, nanoparticle size, shape, and contamination, which result from a large difference in redox priority of metal precursors, intrinsic properties of metals, increasedreactivity of nanocrystallites, and interactions with constituents for the synthesis such as solvent, stabilizer, and reducing agent, etc. Carbon-supported Pt-Ni alloy nanoparticles were prepared by the borohydride reduction method in anhydrous solvent. Pt-Ru alloy nanoparticles supported on carbon black were also prepared by the similar synthetic method to that of Pt-Ni. Since electrocatalytic reactions are strongly dependent on the surface structure of metal catalysts, the atom-leveled design of the surface structure plays a significant role in a high catalytic activity and the utilization of electrocatalysts. Therefore, surface-modified electrocatalysts have attracted much attention due to their unique structure and new electronic and electrocatalytic properties. The carbon-supported Au and Pd nanoparticles were adapted as the substrate and the successive reduction process was used for depositing Pt and PtM (M=Ru, Pd, and Rh) bimetallic elements on the surface of Au and Pd nanoparticles. Distinct features of the overlayers for electrocatalytic activities including methanol oxidation, formic acid oxidation, and oxygen reduction were investigated.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 춘계학술대회
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• pp.141-145
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• 2007

Due to their excellent catalytic activity with respect to methanol oxidation on platinum at low temperature, platinum nanosized catalysts have been a topic of great interest for use in direct methanol fuel cells (DMFCs). Since pure platinum is readily poisoned by CO, a by-product of methanol electrooxidation, and is extremely expensive, a number of efforts to design and characterize Pt-based alloy nanosized catalysts or Pt nanophase-support composites have been attempted in order to reduce or relieve the CO poisoning effect. In this review paper, we summarize these efforts based upon our recent research results. The Pt-based nanocatalysts were designed by chemical synthesis and thin-film technology, and were characterized by a variety of analyses. According to bifunctional mechanism, it was concluded that good alloy formation with $2^{nd}$ metal (e.g., Ru) as well as the metallic state and optimum portion of Ru element in the anode catalyst contribute to an enhanced catalytic activity for methanol electrooxidation. In addition, we found that the modified electronic properties of platinum in Pt alloy electrodes as well as the surface and bulk structure of Pt alloys with a proper composition could be attributed to a higher catalytic activity for methanol electooxdation. Proton conducting contribution of nanosized electrocatalysts should also be considered to be excellent in methanol electrooxidation (Spillover effect). Finally, we confirmed the ensemble effect, which combined all above effects, in Pt-based nanocatalsyts especially, such as PtRuRhNi and $PtRuWO_{3}$, contribute to an enhanced catalytic activity.

• 폴리머
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• 제35권1호
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• pp.35-39
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• 2011

본 연구에서는 고분자 전해질 연료전지의 타소 지지체로 중형기공 실리카(SBA-15)를 이용한 전통적인 주형합성법을 이용하여 중형기공 탄소(CMK-3)를 합성하였다. 합성된 CMK-3는 추가적으로 비표면적과 물리적 성질을 증가시키기 위하여 활성화제로 수산화 칼륨 (KOH)양을 0, 1, 3, 및 4g으로 달리하여 활성화하였다. 그리고 활성화된 CMK-3(K-CMK-3)에 화학적 환원 방법을 이용하여 백금과 루테늄을 답지하였다. CMK-3에 담지된 백금-루테늄 촉매의 특성을 확인하기 위해 비표면적 장치(BET), X-선 회절분석법(XRD), 주사전자현미경(SEM), 투과전자현미정(TEM), 유도결합 플라즈마 질량분석기(ICP-MS)를 이용하였다. 또한, 백금 루테늄 촉매의 전기화학적인 특성을 순환전류전압 실험으로 분석하였다. 결론적으로, 3 g의 KOH로 활성화된 CMK-3(K3g-CMK-3)가 가장 넓은 비표면적을 나타냈다. 또한, K3g-CMK-3의 높은 비표면적은 백금-루테늄의 균일한 분산과 함께 전기적인 촉매의 성능을 향상시키는 것을 확인할 수 있었다.

• 전기화학회지
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• 제11권3호
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• pp.141-146
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• 2008

안티몬 도핑된 주석 산화물(ATO)에 담지된 백금 촉매(Pt/ATO)의 에탄올 산화반응에 대한 활성과 전기화학적 안정성을 평가하였다. Pt 콜로이드 입자를 ATO 입자에 담지하여 Pt/ATO 촉매를 제조하였으며, 제조된 촉매는 X-ray diffraction, transmission electron microscopy (TEM), 그리고 cyclic voltammetry를 이용하여 평가하였다. Pt/ATO 촉매의 에탄올 산화 활성은 Pt/C, PtRu/C에 비해 크게 우수하였다. Pt/ATO 촉매의 전기화학적 안정성 또한 Pt/C에 비해 우수하였으며, TEM 사진을 통하여 확인한 결과 Pt/ATO의 안정성은 Pt입자의 성장 속도가 Pt/C에 비해 느리기 때문인 것으로 확인되었다. 위의 결과로부터 ATO 나노입자가 직접 에탄올 연료전지용 담지체로서, 활성 및 안정성 향상을 기대할 수 있는 물질임을 확인하였다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.132-132
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• 2013

Colloidal synthesis of nanoparticles with well-controlled size, shape, and composition, together with development of in situ surface science characterization tools, such as ambient pressure X-ray photoelectron spectroscopy (APXPS), has brought new opportunities to unravel the surface structure of working catalysts. Recent studies suggest that surface oxides on transition metal nanoparticles play an important role in determining the catalytic activity of CO oxidation. In this talk, I will outline the recent studies on the influence of surface oxides on Rh, Pt, Ru and Co nanoparticles on the catalytic activity of CO oxidation [1-3]. Transition metal nanoparticle model catalysts were synthesized in the presence of poly(vinyl pyrrolidone) polymer capping agent and deposited onto a flat Si support as two-dimensional arrays using the Langmuir-Blodgett deposition technique. APXPS studies exhibited the reversible formation of surface oxides during oxidizing, reducing, and CO oxidation reaction [4]. General trend is that the smaller nanoparticles exhibit the thicker surface oxides, while the bigger ones have the thin oxide layers. Combined with the nature of surface oxides, this trend leads to the different size dependences of catalytic activity. Such in situ observations of metal nanoparticles are useful in identifying the active state of the catalysts during use and, hence, may allow for rational catalyst designs for practical applications. I will also show that the surface oxide can be engineered by using the simple surface treatment such as UV-ozone techniques, which results in changing the catalytic activity [5]. The results suggest an intriguing way to tune catalytic activity via engineering of the nanoscale surface oxide.