• Bulletin of the Korean Chemical Society
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• v.33 no.10
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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).

• 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.

• 한국전기화학회:학술대회논문집
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• 2001.06a
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• pp.37-42
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• 2001

The electrooxidation of methanol was studied using Pt, PtNi(1.1 and 3:1), PtRuNi and PtRu(1:1) alloy nanoparticles in sulfuric acid solution for application to a direct methanol fuel cell. The PtNi and PtRuNi alloys showed excellent catalytic activities compared to those of pure Pt and PtRu. The role of Ni in the electrocatalytic activity was investigated using cyclic voltammetry (CV), chronoamperometry (CA), X-ray photoelectron spectroscopy (XPS). The XPS data confirm that the chemical states of Pt are exclusively metal as well as the presence of metallic Ni, NiO, $Ni(OH)_2$, NiOOH, metallic Ru, $RuO_2$, and $RuO_3$. Negative shifts of the binding energies of Pt for the PtNi alloy nanoparticles were determined by XPS measurements. This can be explained based by assuming that the enhanced activities of PtNi alloys for methanol electrooxidation were caused by the oxide states of Ni and by the change in the electronic structure of Pt component in the alloys.

• Carbon letters
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• v.14 no.2
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• pp.121-125
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• 2013

In this study, PtRu nanoparticles deposited on binary carbon supports were developed for use in direct methanol fuel cells using carbon blacks (CBs) and multi-walled carbon nanotubes (MWCNTs). The particle sizes and morphological structures of the catalysts were analyzed using X-ray diffraction and transmission electron microscopy, and the PtRu loading content was determined using an inductively coupled plasma-mass spectrometer. The electrocatalytic characteristics for methanol oxidation were evaluated by means of cyclic voltammetry with 1 M $CH_3OH$ in a 0.5 M $H_2SO_4$ solution as the electrolyte. The PtRu particle sizes and the loading level were found to be dependent on the mixing ratio of the two carbon materials. The electroactivity of the catalysts increased with an increasing MWCNT content, reaching a maximum at 30% MWCNTs, and subsequently decreased. This was attributed to the introduction of MWCNTs as a secondary support, which provided a highly accessible surface area and caused morphological changes in the carbon supports. Consequently, the PtRu nanoparticles deposited on the binary support exhibited better performance than those deposited on the single support, and the best performance was obtained when the mass ratio of CBs to MWCNTs was 70:30.

• 한국전기화학회:학술대회논문집
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• 2002.07a
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• pp.179-182
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• 2002

The electrooxidation of methanol was studied using Pt, PtRu(1:1), PtNi(1:1), PtRh(1:1) and PtOs(1:1) alloy nanoparticles for application as electrocatalysts. The effects of the second metals in the electrocatalytic activity was investigated using cyclic voltammetry (CV), chronoamperometry (CA), X-ray photoelectron spectroscopy (XPS). There are the metallic and oxygen states in the PtRu and PtOs electrocatalysts . In the XPS of PtRu and PtOs alloy nanoparticles, the oxygen sources were dominant as the second metal's effects. Negative shifts of the binding energies of Pt for the PtNi, PtRh alloy nanoparticles were determined by XPS measurements, which can be explained by electronic effects.

• Analytical Science and Technology
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• v.19 no.4
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• pp.333-341
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• 2006

PVP-protected Ag, Pd and $Pt_{50}-Ru_{50}$ colloids were prepared independently by using ${\gamma}$-irradiation and electron beam (EB) at ambient temperature. UV-visible spectra of these colloids show the characteristic bands of surface resonance and give evidence for the formation of nanoparticles. Transmission electron microscopy (TEM) experiments were used to know the morphology of nanoparticles prepared by ${\gamma}$-irradiation and EB. The size of Ag, Pd, and $Pt_{50}-Ru_{50}$ nanoparticles prepared by ${\gamma}$-irradiation was ca. 13, 2-3, 15 nm, respectively. While, the size of Ag, Pd, and $Pt_{50}-Ru_{50}$ nanoparticles prepared by EB was ca. 10, 6, and 1-3 nm, respectively. Cyclic voltamograms (CV) were recorded for the Au electrodes immobilized with these nanoparticles. CVs indicated the modifications in the surface as a result of immobilization.

• Analytical Science and Technology
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• v.26 no.1
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• pp.42-50
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• 2013

This paper describes the electrocatalytic activity for the oxidation of small biomolecules on the surface of Pt-Ru nanoparticles supported by $TiO_2$-hollow sphere prepared for use in sensor applications or fuel cells. The $TiO_2$-hollow sphere supports were first prepared by sol-gel reaction of titanium tetraisopropoxide with poly(styrene-co-vinylphenylboronic acid), PSB used as a template. Pt-Ru nanoparticles were then deposited by chemical reduction of the $Pt^{4+}$ and $Ru^{3+}$ ions onto $TiO_2$-hollow sphere ($Pt-Ru@TiO_2-H$). The prepared $Pt-Ru@TiO_2-H$ nanocomposites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and elemental analysis. The electrocatalytic efficiency of Pt-Ru nanoparticles was evaluated via ethanol, methanol, dopamine, ascorbic acid, formalin, and glucose oxidation. The cyclic voltammograms (CV) obtained during the oxidation studies revealed that the $Pt-Ru@TiO_2-H$ nanocomposites showed high electrocatalytic activity for the oxidation of biomolecules. As a result, the prepared Pt-Ru catalysts doped onto $TiO_2$-H sphere nanocomposites supports can be used for non-enzymatic biosensor or fuel cell anode electrode.

• 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 the Korean Chemical Society
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• v.64 no.1
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• pp.49-53
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• 2020

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.159-159
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• 2009

In this work, nitrogen and oxygen functionalities was introduced to the graphite nanofibers (GNFs) and their effect on electrocatalytic performance of the GNF supports for direct methanol fuel cells (DMFCs) was invesigated. The nitrogen and oxygen groups were introduced through the urea treatments and acid treatment, respectively. And, PtRu catalysts deposited on modified GNFs were prepared by a chemical reduction method. The catalysts were characterized by means of elemental analysis, nitrogen adsorption, and X-ray photoelectron spetroscopy (XPS). The structure and morphological characteristics of the catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). As a result, the Pt-Ru nanoparticles were impregnated on GNFs with good formation in 3-5 nm. And, the cyclic voltammograms for methanol oxidation revealed that the methanol oxidation peak varied depending on changes of surface functional groups. It was thus considered that the PtRu deposition was related to the reduction of PtRu and surface characteristics of the carbon supports. The changes of surface functional groups were related to PtRu reduction, significantly affect the methanol oxidation activity of anode electrocatalysts in DMFCs.