Pt/C catalysts were prepared using black carbon (CB), and evaluated for their potential application as a catalyst of liquid-phase catalystic exchange for tritium treatment. CB was treated with 10% H2O2 solution for 0 and 2 hours at 105°C, Ethylene glycol and 40wt% Pt were added to the dried treated sample to prepare a Pt/C catalyst. The physical and chemical properties of the prepared catalysts were evaluated by BET, XRD, elemental analysis (EA), and TEM analyses. As a result of BET analysis, the surface area of CB without 10% H2O2 was 237.2 m2·g-1, and after treatment with 10% H2O2, it decreased to 181.2 m2·g-1 for 2 hours. However, the internal surface area increased, indicating the possibility that more Pt could be distributed inside the CB treated with 10% H2O2. In the XRD analysis results, the presence of Pt was confirmed by observing the Pt peak in the prepared Pt/C catalyst, and it was also observed through TEM analysis that Pt was evenly distributed within the CB. The elemental analysis (EA) results showed that the ratio of S and N decreased and the ratio of O increased with increasing 10% H2O2 treatment time. The H2O2 treated carbon supported Pt catalysts and polytetrafluoroethylene were then loaded together on a foamed nickel carrier to obtain hydrophobic catalysts. Our hydrophobic Pt catalyst using H2O2 treated black carbon are expected to be usefully used in the tritium treatment system.

The poor durability issue of polymer electrolyte membrane fuel cells is a major concern in terms of their commercialization. To understand the degradation mechanism of the catalysts, an accelerated durability test (ADT) was conducted according to the protocol established by internationally accredited organizations. However, reversible and irreversible factors contributing to the loss of activity have not yet been practically segregated because of the limitations of a batch-type three-electrode system, leading to the misunderstanding of the deactivation mechanism. In this study, we investigated the effect of a fresh electrolyte on the ADT and recovery process. When the fresh electrolyte was used at every range of the cycle, the chances of incorrect detection of dissolved CO and Pt ions in the electrolyte were very low. When the same electrolyte was used throughout the test, the accumulated Pt ions were deposited on the surface of the Pt nanoparticles or carbon support, affording an increased electrochemical surface area (ECSA) of Pt. Therefore, we believe that periodic replacement by a fresh electrolyte or a continuous-flow electrolyte is essential for the precise determination of the structural and electrochemical changes in Pt/C catalysts.

We have studied a method to prepare polydopamine-modified reduced graphene oxide-supported Pt nanoparticles (Pt– PDA–RGO). The Pt–PDA–RGO nanocomposites were synthesized by a wet-coating process, which was induced by selfpolymerization of dopamine. As an eco-friendly and versatile adhesive source in nature, dopamine could be easily adhered to surfaces of organic material and inorganic material via polymerization processes and spontaneous adsorption under weak alkaline pH conditions. To apply the unique features of dopamine, we synthesized Pt–PDA–RGO nanocomposites with a different quantity of dopamine, which are expected to preserve the improved Pt adsorption on graphene, resulting in the enhanced electrocatalytic performance. The morphology and micro-structure were examined by field emission scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Compared to pristine Pt–deposited RGO (Pt–RGO), Pt–PDA–RGO (30 wt% dopamine against RGO) nanocomposites showed a superior electrochemical active surface area for a methanol oxidation. This could be related to the fact that the optimized c

Nitrogen (N)-doped protein-based carbon as platinum (Pt) catalyst supports from tofu for oxygen reduction reactions are synthesized using a carbonization and reduction method. We successfully prepare 5 wt% Pt@N-doped protein-based carbon, 10 wt% Pt@N-doped protein-based carbon, and 20 wt% Pt@N-doped protein-based carbon. The morphology and structure of the samples are characterized by field emission scanning electron microscopy and transmission electron micro scopy, and crystllinities and chemical bonding are identified using X-ray diffraction and X-ray photoelectron spectroscopy. The oxygen reduction reaction are measured using a linear sweep voltammogram and cyclic voltammetry. Among the samples, 10 wt% Pt@N-doped protein-based carbon exhibits exellent electrochemical performance with a high onset potential of 0.62 V, a high E1/2 of 0.55 V, and a low ΔE1/2= 0.32 mV. Specifically, as compared to the commercial Pt/C, the 10 wt% Pt@N-doped proteinbased carbon had a similar oxygen reduction reaction perfomance and improved electrochemical stability.

금속 산화물과 혼합한 Pt-Sn/Al2O3 촉매의 프로판 탈수소 반응 성능의 향상 가능성에 대해 서 연구하였다. 금속 산화물로서 Cu-Mn/γ-Al2O3, Ni-Mn/γ-Al2O3, Cu/α-Al2O3를 제조하여 Pt-Sn/Al2O3 촉매와 혼합하고, 프로판 탈수소 반응 성능을 측정하였다. 이 결과들을 불활성 물질인 glass bead를 혼합한 Pt-Sn/Al2O3 촉매를 기준샘플로 삼아 비교하였다. 촉매와 금속산화물을 환원처리 하지 않고 반응 실험한 경우, 576.5℃에서 기준샘플의 전환율 8% 대비, Cu-Mn/γ-Al2O3를 혼합한 Pt-Sn/Al2O3 촉매가 14.9%의 높은 전환율과 96.8%의 선택도를 보였다. 촉매와 금속산화물을 환원 처 리하여 반응활성을 측정한 경우, Cu/α-Al2O3과 Pt-Sn/Al2O3의 혼합촉매가 기준샘플대비 초기에 높은 수율을 보였다. 그러나, 촉매를 환원 처리한 경우 전반적으로 전환율 상승이 크지 않았고, 이것으로 Cu-Mn/γ-Al2O3의 격자산소가 탈수소반응의 전환율 증가 영향을 주었음을 알 수 있었다.

Pt@Cu/C core-shell catalysts were successfully prepared by impregnation of a carbon support with copper precursor, followed by transmetallation between platinum and copper. The Pt@Cu/C core-shell catalysts retained a core of copper with a platinum surface. The prepared catalysts were used for hydrogen production through catalytic dehydrogenation of decalin for eventual application to an onboard hydrogen supply system. Pt@Cu/C core-shell catalysts were more efficient at producing hydrogen via decalin dehydrogenation than Pt/C catalysts containing the same amount of platinum. Supported coreshell catalysts utilized platinum highly efficiently, and accordingly, are lower-cost than existing platinum catalysts. The combination of impregnation and transmetallation is a promising approach for preparation of Pt@Cu/C core-shell catalysts.

Carbon-supported Pt catalyst systems containing defect adsorption sites on the anode of direct methanol fuel cells were investigated, to elucidate the mechanisms of H2 dissociation and carbon monoxide (CO) poisoning. Density functional theory calculations were carried out to determine the effect of defect sites located neighboring to or distant from the Pt catalyst on H2 and CO adsorption properties, based on electronic properties such as adsorption energy and electronic band gap. Interestingly, the presence of neighboring defect sites led to a reduction of H2 dissociation and CO poisoning due to atomic Pt filling the defect sites. At distant sites, H2 dissociation was active on Pt, but CO filled the defect sites to form carbon π-π bonds, thus enhancing the oxidation of the carbon surface. It should be noted that defect sites can cause CO poisoning, thereby deactivating the anode gradually.

To improve the methanol electro-oxidation in direct methanol fuel cells(DMFCs), Pt electrocatalysts embedded on porous carbon nanofibers(CNFs) were synthesized by electrospinning followed by a reduction method. To fabricate the porous CNFs, we prepared three types of porous CNFs using three different amount of a styrene-co acrylonitrile(SAN) polymer: 0.2 wt%, 0.5 wt%, and 1 wt%, respectively. A SAN polymer, which provides vacant spaces in porous CNFs, was decomposed and burn out during the carbonization. The structure and morphology of the samples were examined using field emission scanning electron microscopy and transmission electron microscopy and their surface area were measured using the Brunauer- Emmett-Teller(BET). The crystallinities and chemical compositions of the samples were examined using X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical properties on the methanol electro oxidation were characterized using cyclic voltammetry and chronoamperometry. Pt electrocatalysts embedded on porous CNFs containing 0.5 wt% SAN polymer exhibited the improved methanol oxidation and electrocatalytic stability compared to Pt/conventional CNFs and commercial Pt/ C(40 wt% Pt on Vulcan carbon, E-TEK).

Pt nanoparticle catalysts incorporated on RuO2 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 RuO2 nanowire support via an electrospinning method, two different types of incorporated Pt nanoparticle electrocatalysts were prepared using a precipitation method via the reaction with NaBH4 as a reducing agent. One electrocatalyst was 20 wt% Pt/RuO2, and the other was 40 wt% Pt/RuO2. The structural and electrochemical properties of the Pt nanoparticle electrocatalysts incorporated on electrospun RuO2 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 RuO2 nanowire support with a diameter of approximately 50 nm. The cyclic voltammetry results showed that the Pt nanoparticle catalysts incorporated on the electrospun RuO2 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 RuO2 nanowire support. Therefore, the Pt nanoparticle catalysts incorporated on the electrospun RuO2 nanowire support could be a promising electrode for direct methanol fuel cells (DMFCs).

This study is aimed to increase the activity of cathodic catalysts for PEMFCs(Polymer Electrolyte Membrane Fuel Cells). we investigated the temperature effect of 20wt% Pt/C catalysts at five different temperatures. The catalysts were synthesized by using chemical reduction method. Before adding the formaldehyde as reducing agent, process was undergone for 2 hours at the room temperature (RT), 40˚C, 60˚C, 80˚C and 100˚C, respectively. The performances of synthesize catalysts are compared. The electrochemical oxygen reduction reaction (ORR) was studied on 20wt% Pt/C catalysts by using a glassy carbon electrode through cyclic voltammetric curves (CV) in a 1M H2SO4 solution. The ORR specific activities of 20wt% Pt/C catalysts increased to give a relative ORR catalytic activity ordering of 80˚C > 100˚C > 60˚C > 40˚C > RT. Electrochemical active surface area (EAS) was calculated with cyclic voltammetry analysis. Prepared Pt/C (at 80˚C, 100˚C) catalysts has higher ESA than other catalysts. Physical characterization was made by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The TEM images of the carbon supported platinum electrocatalysts (80˚C, 100˚C) showed homogenous particle distribution with particle size of about 2~3.5 nm. We found that a higher reaction temperature resulted in more uniform particle distribution than lower reaction temperature and then the XRD results showed that the crystalline structure of the synthesized catalysts are seen FCC structure.

Nanosized Pt, Pt-Ru and Pt-CeO2 electrocatalysts supported on acid-treated carbon nanotube (CNT) were synthesized by microwave-assisted heating of polyol process using H2Cl6Pt·6H2O, RuCl3, CeCl3 precursors, respectively, and were characterized by XRD and TEM. And then the electrochemical activity of methanol oxidation for catalyst/CNT nanocomposite electrodes was investigated. The microwave assisted polyol process produced the nano-sized crystalline catalysts particles on CNT. The size of Pt supported on CNT was 7~12 nm but it decreased to 3~5 nm in which 10wt% sodium acetate was added as a stabilizer during the polyol process. This fine Pt catalyst particles resulted in a higher current density for Pt/CNT electrode. It was also found that 10 nm size of PtRu alloys were formed by polyol process and the onset potential decreased with Ru addition. Cyclic voltammetry analysis revealed that the Pt75Ru25/CNT electrode had the highest electrochemical activity owing to a higher ratio of the forward to reverse anodic peak current. And the chronoamperemetry test showed that Pt75Ru25 catalyst had a good catalyst stability. The activity of Pt was also found to be improved with the addition of CeO2.

Different oxidation treatments on CNTs using diluted 4.0 M H2SO4 solution at room temperature and or at 90℃ reflux conditions were investigated to elucidate the physical and chemical changes occurring on the treated CNTs, which might have significant effects on their performance as catalyst supports in PEM fuel cells. Raman spectroscopy, X-ray diffraction and transmission electron microscope analyses were made for the acid treated CNTs to determine the particle size and distribution of the CNT-supported Pt-Ru nanoparticles. These CNT-supported Pt-based nanoparticles were then employed as anode catalysts in PEMFC to investigate their catalytic activity and single-cell performance towards H2 oxidation. Based on PEMFC performance results, refluxed Pt-Ru/CNT catalysts prepared using CNTs treated at 90℃ for 0.5 h as anode have shown better catalytic activity and PEMFC polarization performance than those of the commercially available Pt-Ru/C catalyst from ETEK and other Pt-Ru/CNT catalysts developed using raw CNT, thus demonstrating the importance of acid treatment in improving and optimizing the surface properties of catalyst support.

Carbon supported electrocatalysts are commonly used as electrode materials for polymer electrolyte membrane fuel cells(PEMFCs). These kinds of electrocatalysts provide large surface area and sufficient electrical conductivity. The support of typical PEM fuel cell catalysts has been a traditional conductive type of carbon black. However, even though the carbon particles conduct electrons, there is still significant portion of Pt that is isolated from the external circuit and the PEM, resulting in a low Pt utilization. Herein, new types of carbon materials to effectively utilize the Pt catalyst are being evaluated. Carbon nanofiber/activated carbon fiber (CNF/ACF) composite with multifunctional surfaces were prepared through catalytic growth of CNFs on ACFs. Nickel nitrate was used as a precursor of the catalyst to synthesize carbon nanofibers(CNFs). CNFs were synthesized by pyrolysising CH4 using catalysts dispersed in acetone and ACF(activated carbon fiber). The as-prepared samples were characterized with transmission electron microscopy(TEM), scanning electron microscopy(SEM). In TEM image, carbon nanofibers were synthesized on the ACF to form a three-dimensional network. Pt/CNF/ACF was employed as a catalyst for PEMFC. As the ratio of prepared catalyst to commercial catalyst was changed from 0 to 50%, the performance of the mixture of 30 wt% of Pt/CNF/ACF and 70wt% of Pt/C commercial catalyst showed better perfromance than that of 100% commercial catalyst. The unique structure of CNF can supply the significant site for the stabilization of Pt particles. CNF/ACF is expected to be promising support to improve the performance in PEMFC.

Pt-loaded carbon black for the catalyst of a PEM fuel cell was synthesized with different molar ratios of polyvinylpyrrolidone and H2PtCl6 solution to improve the dispersion of Pt nanoparticles on carbon black and decrease the size of Pt nanoparticles. From transmission electron microscopy results, Pt nanoparticles of a size of approximately 2 nm were highly dispersed when the polyvinylpyrrolidone concentration was 10mM. The electrochemical activity of the synthesized Pt/C catalysts was investigated by cyclic voltammetry, showing that the as-synthesized Pt-loaded carbon black catalyst had the best activity at a polyvinylpyrrolidone concentration of 10 mM.

고분자전해질형 연료전지에서 촉매의 활성을 증가시키기 위하여 기존에 사용되고 있는 백금과 전이금속인 chromium, nickel과의 합금을 제조하였다. XRD를 이용하여 합금의 구조가 33˚에서 superlattice line을 가지고 있는 것으로 보아 face centered cubic 구조를 가진 ordered alloy로 이루어졌다는 것을 알 수 있었다. 열처리 온도가 증가할수록 합금의 입자 크기는 증가하였으며, 결정 격자 상수는 감소하였다. 전지성능테스트, cyclic voltammogram 등을 통하여 mass activity, specific activity, Tafel slope, 개회로 전압을 측정한 결과, 합금촉매의 활성이 순수한 백금촉매보다 크게 향상되었음을 알 수 있었다.

The present work has been devoted to the catalytic reduction of N2O by H2 with Pt/SiO2 catalysts at very low temperatures, such as 110oC, and their nanoparticle sizes have been determined by using H2-N2O titration, X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM) measurements. A sample of 1.72% Pt/SiO2, which had been prepared by an ion exchange method, consisted of almost atomic levels of Pt nanoparticles with 1.16 nm that are very consistent with the HRTEM measurements, while a Pt/SiO2 catalyst possessing the same Pt amount via an incipient wetness technique did 13.5 nm particles as determined by the XRD measurements. These two catalysts showed a noticeable difference in the on-stream deN2O activity maintenance profiles at 110℃. This discrepancy was associated with the nanoparticle sizes, i.e., the Pt/SiO2 catalyst with the smaller particle size was much more active for the N2O reduction. When repeated measurements of the N2O reduction with the 1.16 nm Pt catalyst at 110oC were allowed, the catalyst deactivation occurred, depending somewhat on regeneration excursions.

Simulated waste-derived synthesis gas has been tested for hydrogen production through water gas shift (WGS) reaction in the temperature range of 240oC ~ 400oC over supported Pt catalysts prepared by an incipient wetness impregnation method. MG30, MgO, ZrO2, Al2O3 and CeO2 were employed as supports for WGS reaction in this study. 1 wt.% Pt/ CeO2 catalyst exhibited the highest CO conversion as well as 100% CO2 selectivity. This is due to easier reducibility of Pt/CeO2 and high oxygen mobility and oxygen storage capacitiy of CeO2. Pt/CeO2 catalyst can be a promising catalyst for WGS reaction from waste-derived synthesis gas.

TiO2- and SiO2-supported Co3O4, Pt and Co3O4-Pt catalysts have been studied for CO and C3H8 oxidations at temperatures less than 250℃ which is a lower limit of light-off temperatures to oxidize them during emission test cycles of gasoline-fueled automotives with TWCs (three-way catalytic converters) consisting mainly of Pt, Pd and Rh. All the catalysts after appropriate activation such as calcination at 350℃ and reduction at 400℃ exhibited significant dependence on both their preparation techniques and supports upon CO oxidation at chosen temperatures. A Pt/TiO2 catalyst prepared by using an ion-exchange method (IE) has much better activity for such CO oxidation because of smaller Pt nanoparticles, compared to a supported Pt obtained via an incipient wetness (IW). Supported Co3O4-only catalysts are very active for CO oxidation even at 100℃, but the use of TiO2 as a support and the IW technique give the best performances. These effects on supports and preparation methods were indicated for Co3O4-Pt catalysts. Based on activity profiles of CO oxidation at 100℃ over a physical mixture of supported Pt and Co3O4 after activation under different conditions, and typical light-off temperatures of CO and unburned hydrocarbons in common TWCs as tested for C3H8 oxidation at 250℃ with a Pt-exchanged SiO2 catalyst, this study may offer an useful approach to substitute Co3O4 for a part of platinum group metals, particularly Pt, thereby lowering the usage of the precious metals.