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

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.08a
• /
• pp.212-212
• /
• 2011

In addition to the catalysts' activity and selectivity, the deactivation of catalysts during use is of practical importance. It is crucial to understand the phenomena of the deactivation to predict the loss of activity during catalyst usage so that the high operational costs associated with catalyst replacement can be reduced. In this study, the activity of Ru catalysts, such as nanoparticles (3~6 nm) and polycrystalline thin film (50 nm), have been investigated under CO oxidation and oxidative/reductive reaction conditions at various temperatures with the ambient pressure X-Ray photoelectron spectroscopy (APXPS). With APXPS, the surface oxides on the catalyst are measured and monitored in-situ. It was found that the Ru film exhibited faster oxidation-and-reduction compared to that of nanoparticles showing mild oxidative-and-reductive characteristics. Additionally, the larger Ru nanoparticles showed a higher degree of oxide formation at all temperatures, suggesting a higher stability of the oxide. These observations are in agreement with the catalytic activity of Ru catalysts. The loss of activity of Ru films is correlated with bulk oxide formation, which is inactive in CO oxidation. The Ru nanoparticle, however, does not exhibit deactivation under similar conditions, suggesting that its surface is covered with a highly active ultrathin surface oxide. Since the active oxide is more stable as nanoparticles than as a film, the nanoparticles showed mild oxidative/reductive behavior, as confirmed by APXPS results. We believe these simultaneous observations of both the surface oxide of Ru catalysts and the reactivity in real time enable us to pinpoint the deactivation phenomena more precisely and help in designing more efficient and stable catalytic systems.

• 한국신재생에너지학회:학술대회논문집
• /
• 2005.06a
• /
• pp.296-298
• /
• 2005

Hydrogen generation by the hydrolysis of aqueous sodium borohydride $(NaBH_4)$ solutions was studied using IRA-400 anion resin dispersed Pt. Ru catalysts and Lithium Cobalt oxide $(LiCoO_2)$ supported Pt, Ru and PtRu catalysts. The performance of the $LiCoO_2$ supported catalysts is better than the ion exchange resin dispersed catalysts. There is a marked concentration dependence on the performance of the $LiCoO_2$ supported catalysts and the hydrogen generation rate goes down if the borohydride concentration is increased beyond $10\%$. The efficiency of PtRu- $LiCoO_2$ is almost double that of either Ru-$LiCoO_2$ or Pt-$LiCoO_2$ for $NaBH_4$ concentrations up to $10\%$.

• 한국신재생에너지학회:학술대회논문집
• /
• 2011.11a
• /
• pp.97.2-97.2
• /
• 2011

Pt-Ru and Pt-Ni bimetallic catalysts were prepared and tested for heavy hydrocarbon reforming. Metals were supported on CGO($Ce_{0.8}Gd_{0.2}O_{2.0-x}$) by incipient wetness method. The prepared catalysts were characterized by Temperature programmed reduction(TPR). Oxidative steam reforming of n-dodecane was conducted to compare the activity of the catalysts. The reforming temperature was varied from $500^{\circ}C$ to $800^{\circ}C$ at fixed $O_2$/C of 0.3, $H_2O$/C of 3.0 and GHSV of 5,000/h.Reduction peaks of metal oxide, surface CGO and bulk CGO were detected. Reduction temperature of metal oxide decreased over the bi-metallic catalysts. It is considered that interaction between metals leads to decrease interaction between metal and oxygen. On the other hands, reduction temperatures of surface CGO were dectected in the order of Pt-Ru > Pt-Ni > Pt. low reduction temperatures of surface CGO indicates the low activation energy for oxygen ion conduction to metal. Oxygen ion conduction is known as de-coking mechanism of ionic conducting supports such as CGO. In activity test, fuel conversion was in the same order of Pt-Ru > Pt-Ni > Pt. Especially, 100% of fuel conversion was obtained over Pt-Ru catalysts at $500^{\circ}C$.

• Particle and aerosol research
• /
• v.8 no.2
• /
• pp.69-74
• /
• 2012

This study describes how successfully a conventional flame aerosol synthesis was used to continuously synthesize Pt-Ru catalysts supported by carbon agglomerates. Nearly spherical catalysts produced in the flame were mainly composed of metallic Pt and Ru with the molar ratio of 1:1 and those sizes were controllable from ~1.5 nm to ~2.0 nm. Nevertheless, only Pt peaks were found from X-ray diffraction experiments, suggesting that amorphous-like Ru was well mixed in the crystalline Pt lattices. It was found from Cyclo-voltamograms and CO stripping experiments that the electrochemical properties of the catalysts are at least comparable to that of a conventional commercial sample.

• 한국신재생에너지학회:학술대회논문집
• /
• 2009.06a
• /
• pp.369-372
• /
• 2009

In the present study, the effect of chemical treatment on graphite nanofibers (GNFs) supports with various concentrated nitric acids was investigated for methanol oxidation. To optimize the electrocatalytic activity, PtRu catalysts were deposited on GNF supports by impregnation method. The surface and structural properties of the GNF supports were characterized by X-ray photoelectron spectroscopy (XPS), element analyzer (EA), and X-ray diffraction (XRD). The morphology of the catalysts was observed by means of transmission electron microscopy (TEM). The electrocatalytic activity of PtRu/GNF catalysts was investigated by cyclic voltammetry measurement. As a result, the oxygen functional groups were introduced on the GNF supports and were gradually increased with increasing of concentrated nitric acid, causing the smaller particle size and higher loading level. And the electrocatalytic activity of the catalysts for methanol oxidation was gradually improved. Consequently, it was found that chemical treatments could influence on surface properties of the carbon supports, resulting in enhancing the electrocatalytic activity of the catalysts for DMFCs.

• Applied Chemistry for Engineering
• /
• v.23 no.6
• /
• pp.561-566
• /
• 2012

PtRuW/C catalysts were prepared with the different molar ratios of Pt : Ru : W and their compositions were analyzed by energy dispersive X-ray (EDX). The uniform distribution of particles was observed using transmission electron microscopy (TEM). An average crystalline size of 3.5~5.5 nm was calculated based on x-ray diffraction (XRD) data. The electrochemical properties such as electrochemically active surface areas, current densities, specific activities and poisoning rates, were analyzed via CO stripping, linear sweep voltammetry and chronoamperometry. From the analysis, we observed that ternary alloy catalysts, except $PtRu_2W_2/C$, have higher current densities, specific activities and stabilities than those of commercial binary catalysts. Among all in-house catalysts, Pt5Ru4W/C showed the highest specific activity of $121.05mA{\cdot}m^{-2}$ and the lowest poisoning rate of $0.01%{\cdot}s^{-1}$.

• Journal of the Korean Electrochemical Society
• /
• v.6 no.1
• /
• pp.13-17
• /
• 2003

Cryogel and aerogel Pt-Ru/C were synthesized by the sol-gel process for the electrooxidation of methanol. From XRD analysis, it was found that the catalysts had highly dispersed Pt-Ru alloys on carbon support although high temperature treatments have been conducted. Electrocatalytic activities of 3 type aerogel catalysts were investigated in half cell experiments by cyclic voltammetry. Among them, Phloroglucinol-Formaldehyde(PF) type catalyst shows the highest activity. From the results of deactivation test for each catalysts, the aerogel catalysts are found to have excellent durability compared with those prepared by colloidal method.

• 한국전기화학회:학술대회논문집
• /
• 2002.07a
• /
• pp.211-218
• /
• 2002

In this study, Pt/Pd (1.1), PtPd (2:1) and PtPd (3:1) binary catalysts and Pt/Ru/Pd (5:4:1) ternary catalyst were designed. The catalysts were synthesized by impregnation method using $NaBH_4$ as a reducing agent. A good catalyst for methanol oxidation requires low on-set potential, stable durability and low activation energy. In order to investigate the catalytic activity for the methanol oxidation, electrochemical measurements such as cyclic voltammetry and chronoamperometry were peformed in sulfuric acid with/without methanol solution. In order to calculate the activation energy of the reaction, electrochemical measurements were also tested at different temperatures. For investigation of the structural analysis such as particle size and alloying, X-ray diffraction and transmission electron microscopy analysis were used. In order to identify the role of the Pd and to determine the composition of the surface of the Pt/Pd nanoparticles, X-ray photoelectron spectroscopy (XPS) analysis was investigated. The XPS spectra of Pd showed that Pd appears only as a metallic state in the binary catalysts. The chemical states of Pt in PtPd catalysts are both metallic and oxidative. Polarization curves and power density data were obtained by testing the DMFC unit cell performance of PtPd and PtRuPd catalysts. These data showed that Pt/Pd (2:1) and Pt/Ru/Pd (5:4:1) have better performance than Pt and Pt/Ru, respectively.

• Transactions of the Korean hydrogen and new energy society
• /
• v.32 no.3
• /
• pp.149-155
• /
• 2021

Most of the reformer experiments have been conducted only in high-temperature operation conditions above 700℃. However, to design high efficiency solid oxide fuel cell, it is necessary to test actual reaction performance in mid-temperature (550℃) operation areas. In order to study the operation characteristics and performance of commercial reforming catalysts, a reforming performance experiment was conducted on mid-temperature. The catalysts used in this study are Ni-based FCR-4 and Ru-based RuA, RuAL. Experiments were conducted with a Steam-to-carbon ratio of 2.0 to 3.0 under gas hourly space velocity (GHSV) 2,000 to 5,000 hr-1. As a result, RuA and RuAL catalysts showed similar gas composition to the equilibrium regardless of the reforming temperature. However, the FCR-4 catalyst showed a lower hydrogen yield compared to the equilibrium under high GHSV conditions.