• Journal of Electrochemical Science and Technology
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• v.7 no.1
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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.

• Korean Journal of Materials Research
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• v.28 no.6
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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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.

• Journal of Sensor Science and Technology
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• v.21 no.6
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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.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.18 no.10
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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.

• Korean Journal of Materials Research
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• v.19 no.4
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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.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.153-156
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• 2012

In this study, two different methods were studied to prepare Pt-Pd catalysts for direct methanol fuel cells in order to enhance the electrochemical efficiency. The catalysts were compared with simultaneously deposited Pt-Pd and sequentially deposited Pt-Pd. The electrocatalysts contained 20 wt% of metal loading on carbon black and 1 : 2 of Pt : Pd atomic ratio. Electrochemical properties of the catalysts were compared by measuring cyclic voltammetries and average sizes and lattice parameters were measured by transmission electron microscopy images and x-ray diffraction. As a result, sequentially deposited Pt-Pd/C catalysts showed better electrochemical properties than those of simultaneously deposited Pt-Pd/C catalysts.

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.532-538
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• 2006

The carbonization and activation conditions for the PAN-based ACF of various grade were investigated to obtain the optimun activation condition with high surface area. And the surface properties and the absorption performance of toxic gas for terror were examined toward the PAN-ACF with the highest surface area. In the test results the surface area increased with increase of the activation temperature, but decreased with increase of the carbonization temperature. After carbonization condition ($900^{\circ}C$-15min) and activation condition ($900^{\circ}C$-30 min), we got the ACF with the highest surface area of $1204m^2/g$. In the absorption test of iodine and toxic gas for terror, this ACF showed more excellent absorption performance than the existing carbon-based adsorbent. Also, in order to give the function characteristic for a selective absorption, the stable nanoparticles of the Ag, Pt, Cu, Pd were prepared and impregnated on the PAN-based ACF in replacement of the existing method supporting metal catalysis. And were analyzed the surface characteristics and the $SO_{2}$ adsorption characteristics. In the $SO_{2}$ absorption performance test of the PAN-ACF with the impregnated nanoparticles, it wasn't change breakthrough time of Ag, Pt, Cu nanoparticle supported the PAN-ACF comparing with breakthrough time (326 sec) of the non supported PAN-ACF but Pd nanoparticle supported the PAN-ACF achieved excellent $SO_{2}$ absorption performance which has break-through time 925 sec.

• Korean Journal of Materials Research
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• v.28 no.11
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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.

• Journal of the Korean Electrochemical Society
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• v.15 no.3
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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.