• Journal of Electrochemical Science and Technology
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• 제7권1호
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• pp.27-32
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• 2016

Although the time dependences of the electrocatalytic activities of Pt and Pd nanoparticles during electrochemical operations have been widely studied, the time dependences under nonpolarized conditions have never been investigated in depth. This study reports the changes in the electrocatalytic activities of Pt and Pd nanoparticles with aging in air and in solution. Pt (or Pd) nanoparticle-modified electrodes are obtained by adsorbing citrate-stabilized Pt (or Pd) nanoparticles on amine-modified indium-tin oxide (ITO) electrodes, or by electrodeposition of Pt (or Pd) nanoparticles on ITO electrodes. The electrocatalytic activities of freshly prepared Pt and Pd nanoparticles in the oxygen reduction reaction slowly decrease with aging. The electrocatalytic activities decrease more slowly in solution than in air. An increase in surface contamination may cause electrocatalytic deactivation during aging. The electrocatalytic activities of long-aged Pt (or Pd) nanoparticles are significantly enhanced and recovered by NaBH₄ treatment.

• 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.

• 센서학회지
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• 제21권6호
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• pp.425-428
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• 2012

This paper presents the fabrication and characterization of graphene based hydrogen sensors. Graphene was synthesized by annealing process of Ni/3C-SiC thin films. Graphene was transferred onto oxidized Si substrates for fabrication of chemiresistive type hydrogen sensors. Au electrode on the graphene shows ohmic contact and the resistance is changed with hydrogen concentration. Nanoparticle catalysts of Pd and Pt were decorated. Response factor and response (recovery) time of hydrogen sensors based on the graphene are improved with catalysts. The response factors of pure graphene, Pt and Pd doped graphenes are 0.28, 0.6 and 1.26, respectively, at 50 ppm hydrogen concentration.

• 한국전기전자재료학회논문지
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• 제18권10호
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• pp.917-923
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• 2005

In this paper, effect of catalytic configuration on the sensing properties of $SnO_2$ nanoparticle gas sensitive thick film was investigated. Two types of catalytic configuration, mono and binary, were made on the $SnO_2$ nanoparticle. In case of mono catalytic system, $3 wt\%$ Pd or Pt catalyst was doped onto the $SnO_2$ nanoparticle, respectively. In case of binary catalytic system, Pd and Pt was doped simultaneously with concentration ratio of 1:2 to 2:1 onto the $SnO_2$ nanoparticle. After doping, gas sensitive thick film was printed on alumina substrate and heat-treated at 450 to $600^{\circ}C$. Gas sensing properties was evaluated using 500 to 10,000 ppm $CH_4$ gas. As a result, gas sensitive thick film with binary catalytic system showed unstable phenomena that the gas sensitivity was changed according to aging time. In contrary, the mono catalytic system showed relatively stable phenomena despite of aging time. Especially, gas sensitive thick film doped with $3 wt\%$ Pt catalyst and heat-treated at $500^{\circ}C$ showed good sensing properties such as 0.57 of $R_{3500}/R_{1000}$ and very small variation within $3.5\%$ after aging for 5 hours, and response time was very short less than 20 seconds.

• 한국재료학회지
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• 제19권4호
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• pp.192-197
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• 2009

Carbon nanotubes (CNT) were used as a catalyst support where catalytically active Pd and Pt metal particles decorated the outside of the external CNT walls. In this study, Pd and Pt nanoparticles supported on $HNO_3$-treated CNT were prepared by microwave-assisted heating of the polyol process using $PdCl_2$ and $H_2PtCl_6{\codt}6H_2O$ precursors, respectively, and were then characterized by SEM, TEM, and Raman. Raman spectroscopy showed that the acid treated CNT had a higher intensity ratio of $I_D/I_G$ compared to that of non-treated CNT, indicating the formation of defects or functional groups on CNT after chemical oxidation. Microwave irradiation for total two minutes resulted in the formation of Pd and Pt nanoparticles on the acid treated CNT. The sizes of Pd and Pt nanoparticles were found to be less than 10 nm and 3 nm, respectively. Furthermore, the $SnO_2$ films doped with CNT decorated by Pd and Pt nanoparticles were prepared, and then the $NO_2$ gas response of these sensor films was evaluated under $1{\sim}5\;ppm$ $NO_2$ concentration at $200^{\circ}C$. It was found that the sensing property of the $SnO_2$ film sensor on $NO_2$ gas was greatly improved by the addition of CNT-supported Pd and Pt nanoparticles.

• 공업화학
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• 제23권2호
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• pp.153-156
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• 2012

본 연구에서 직접 메탄올형 연료전지용 담지 촉매의 전기 화학적 효율을 높이기 위하여 담지 촉매의 합성을 위한 2가지 다른 방법을 조사하였다. 담지 촉매에 있어서 합금을 형성하여 동시 담지하는 방법과 금속을 순차적으로 담지하는 방법을 비교하였다. 금속의 총 함량을 20 wt%를 사용하였으며, Pt-Pd의 금속비를 1 : 2로 하였다. 순환 전류-전압곡선(CVs), TEM 이미지와 XRD분석을 이용하여 두가지 다른 방법으로 제조된 촉매 간의 전기화학적 특성, 입자의 평균 크기 및 결정의 구조 변화를 비교 분석하였다. 그 결과, 순차적 금속 담지 촉매가 동시 담지 촉매보다 단위 무게당 산화전류 수치를 나타내어 보다 높은 전기활성 특성을 보였다.

• 공업화학
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• 제17권5호
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• pp.532-538
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• 2006

탄화 및 활성화 조건을 매개체로 여러 등급의 Polyacrylonitrile (PAN)계 ACF (ACF : Activated Carbon Fiber)를 제조하여 최적의 비표면적을 나타내는 활성화 공정을 알아보았고, 가장 큰 비표면적을 갖는 PAN계 ACF에 대한 표면특성 및 독성가스 등에 대한 흡착특성을 분석하였다. 시험결과 활성화 온도가 증가할수록 비표면적이 증가하고 탄화 온도가 감소할수록 비표면적이 감소하였고, $900^{\circ}C$로 15 min간 탄화한 후 $900^{\circ}C$로 30 min간 활성화 공정을 거친 ACF가 $1204m^2/g$의 가장 높은 비표면적을 나타내었고 요오드 및 테러용 독성가스에 대한 흡착 성능시험 결과 기존의 흡착제보다 우수하였다. 또한 선택적 흡착을 위한 기능성을 부여하기 위하여 기존의 금속염을 침적하는 방법을 대체하여 비교적 안정화된 금속나노입자(Ag, Pt, Cu, Pd)를 제조하여 첨착하였고 이에 대한 표면특성 및 $SO_{2}$에 대한 흡착특성을 분석하였다. 금속나노입자 첨착 ACF에 대한 $SO_{2}$ 흡착성능 시험결과 Ag, Pt, Cu 나노입자를 첨착한 ACF는 무첨착 ACF의 파과시간(326 sec)과 비교 할 때 크게 변함이 없었으나 Pd 나노입자를 첨착한 ACF는 파과시간이 925 sec로 $SO_{2}$ 흡착성능이 매우 우수함을 알 수 있었다.

• 한국재료학회지
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• 제28권11호
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• pp.633-639
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• 2018

In anion exchange membrane fuel cells, Pd nanoparticles are extensively studied as promising non-Pt catalysts due to their electronic structure similar to Pt. In this study, to fabricate Pd nanoparticles well dispersed on carbon support materials, we propose a synthetic strategy using mixed organic ligands with different chemical structures and functions. Simultaneously to control the Pd particle size and dispersion, a ligand mixture composed of oleylamine(OA) and trioctylphosphine(TOP) is utilized during thermal decomposition of Pd precursors. In the ligand mixture, OA serves mainly as a reducing agent rather than a stabilizer since TOP, which has a bulky structure, more strongly interacts with the Pd metal surface as a stabilizer compared to OA. The specific roles of OA and TOP in the Pd nanoparticle synthesis are studied according to the mixture composition, and the oxygen reduction reaction(ORR) activity and durability of highly-dispersed Pd nanocatalysts with different particles sizes are investigated. The results of this study confirm that the Pd nanocatalyst with large particles has high durability compared to the nanocatalyst with small Pd nanoparticles during the accelerated degradation tests although they initially indicated similar ORR performance.

• 전기화학회지
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• 제15권3호
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• pp.135-148
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• 2012

Ionic liquids are steadily attracting interests throughout a recent decade and their application is expanding into various fields including electrochemistry due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, wide electrochemical potential window and so on. These features make ionic liquids become an alternative solution for electrodeposition of metals that cannot be electroplated in aqueous electrolytes. In this review, we classify investigated metals into three categories, which are light (Li, Mg), refractory (Ti, Ta) and noble (Pd, Pt, Au) metals, rather than covering the exhaustive list of metals and try to update the recent development in this area. In electrodeposition of light metals, granular fine Li particles were successfully obtained while the passivation of electrodeposited Mg layers is an obstacle to reversible deposition-dissolution process of Mg. In the case of refractory metals, the quality of Ta and Ti deposit particles was effectively improved with addition of LiF and pyrrole, respectively. In noble metal category, EMIM TFSA ionic liquid as an electrolyte for Au electrodeposition was proven to be effective and BMP TFSA ionic liquid developed a smooth Pd deposit. Pt nanoparticle production from ionic liquid droplet in aqueous solution can be cost-effective and display an excellent electrocatalytic activity.