• Applied Biological Chemistry
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• v.39 no.3
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• pp.227-234
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• 1996

4-Methyl-2,6,7-trioxa-1-phosphabicyclo [2,2,2] octane 1-sulfide (BPS), 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2] octane 1-oxide (BPO) and related monocyclic methylphosphates were prepared and the oxidation of BPS with MCPBA in chlorofrom or methanol was carried out to investigate the formation of reactive intermediates and reaction mechanism. BPO was the only product in chloroform while in methanol isomeric monocyclic methylphosphates were formed through opening of bicylic structure with subsequent phosphorylation of methanol by reactive intermediate formed in reaction. Formation of little amount of BPO was also observed. The structure of phosphorylating intermediate was probed with various spectroscopic methods and monocyclic methyl sulfenyl ester was suggested as a possible structure.

• Applied Chemistry for Engineering
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• v.9 no.7
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• pp.956-960
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• 1998

Cu-Zn and Cu-Zn-Ti catalysts for the steam reforming of methanol were prepared. This reaction was carried out at atmospheric pressure, $250^{\circ}C$, steam/methanol molar ratio 1.5, and contact time 0.1 g-cat.hr/mL-feed. In case of the catalyst with 3 mol% of $TiO_2$, the activity was superior to that of catalysts without $TiO_2$. The reaction products were mainly hydrogen and carbon dioxide. It was found that catalytic activity was not related to specific surface area but affected by metallic copper area which was measured by $N_2O$ decomposition and increased with the addition of $TiO_2$ content. XPS and XRD showed that the oxidation state of zinc was not changed during reaction, but oxidation states of copper existed in Cu(0) or Cu(I).

• Journal of Electrochemical Science and Technology
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• v.1 no.1
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• pp.19-24
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• 2010

Alloying degree is an important structural factor of PtRu catalysts for direct methanol fuel cells (DMFC). In this work, carbon supported PtRu catalysts were synthesized by reduction method using anhydrous ethanol as a solvent and $NaBH_4$ as a reducing agent. Using anhydrous ethanol as a solvent resulted in high alloying degree and good dispersion. The morphological structure and crystallanity of synthesized catalysts were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM). CO stripping and methanol oxidation reaction were measured. Due to high alloying degree catalyst prepared in anhydrous ethanol, exhibited low onset potential for methanol oxidation and negative peak shift of CO oxidation than commercial sample. Consequently, samples, applying ethanol as a solvent, exhibited not only enhanced CO oxidation, but also increased methanol oxidation reaction (MOR) activity compared with commercial PtRu/C (40 wt%, E-tek) and 40 wt% PtRu/C prepared in water solution.

• Journal of Electrochemical Science and Technology
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• v.10 no.3
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• pp.284-293
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• 2019

Herein, we report an electrode surface with a hierarchical assembly of wild-type M13 virus nanofibers (M13) to nucleate the AuPt alloy nanostructures by electrodeposition. M13 was pulled on the electrode surface to produce a virus film, and then a layer of sol-gel matrix (SSG) was wrapped over the surface to protect the film, thereby a bio-template was constructed. Blending of metal binding domains of M13 and amine groups of the SSG of the bio-template were effectively nucleate and directed the growth of nanostructures (NSs) such as Au, Pt and AuPt alloy onto the modified electrode surface by electrodeposition. An electrocatalytic activity of the modified electrode toward methanol oxidation in alkaline medium was investigated and found an enhanced mass activity ($534mA/mg_{Pt}$) relative to its controlled experiments. This bio-templated growth of NSs with precise composition could expedite the intention of new alloy materials with tuneable properties and will have efficacy in green energy, catalytic, and energy storage applications.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.171-171
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• 2009

The electrodes are usually made of a porous mixture of carbon-supported platinum and ionomers. $SnO_2$ particles provide as supports that have been used for DMFCs, and it have high catalytic activities toward methanol oxidation. The main advantage of $SnO_2$ supported electrodes is that it has strong chemical interactions with metallic components. The high activity to a synergistic bifunctional mechanism in which Pt provides the adsorption sites for CO, while oxygen adsorbs dissociative on $SnO_2$. The reaction between the adsorbed species occurs at the Pt/$SnO_2$ boundary. The morphological observations were characterized by FESEM and transmission electron microscopy (TEM). $SnO_2$ particles crystallinity was analyzed by the X-ray diffraction (XRD). The surface bonded state of the $SnO_2$ particles and electrode materials were observed by the X-ray photoelectron spectroscopy (XPS). The electric properties of the Pt/$SnO_2$ catalyst for methanol oxidation have been investigated by the cyclic voltametry (CV) in 0.1M $H_2SO_4$ and 0.1M MeOH aqueous solution. The peak current density of methanol oxidation was increased as the $SnO_2$ content in the anode catalysts increased. Pt/$SnO_2$ catalysts improve the removal of CO ads species formed on the platinum surface during methanol electro-oxidation.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3539-3543
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• 2012

Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in $HClO_4$ medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both $[CAB]_o$, and $[substrate]_o$, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

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

• Journal of Electrochemical Science and Technology
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• v.7 no.2
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• pp.146-152
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• 2016

A combined system with PEMFC and reformer is introduced and optimized for the real use of this kind of system in the future. The hydrogen source to operate the PEMFC system is methanol, which needs two parts of methanol reforming reaction and preferential oxidation (PROX) for the hydrogen fuel process in the combined operation PEMFC system. With the optimized methanol steam reforming condition, we tested PROX reactions in various operation temperature from 170 to 270 ℃ to investigate CO concentration data in the reformed gases. Using these different CO concentration, PEMFC performances are achieved at the combined system. Pt/C and Ru promoted Pt/C were catalysts were used for the anode to compare the stability in CO contained gases. The alloy catalyst of PtRu/C shows higher performance and better resistance to CO than the Pt/C at even high CO amount of 200 ppm, indicating a promotion not only to the activity but also to the CO tolerance. Furthermore, in a system point of view, there is a fluctuation in the PEMFC operation due to the unstable fuel supply. Therefore, we also modified the methanol reforming by a scaled up reactor and pressurization to produce steady operation of PEMFC. The optimized system with the methanol reformer and PEMFC shows a stable performance for a long time, which is providing a valuable data for the PEMFC commercialization.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.15 no.1
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• pp.83-93
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• 1982

In this work, lipid oxidation and the kinetics of the oxidation reaction in fried file-fish meat were investigated when sun-dried file-fish was stored under the conditions of various water activities and temperature, 35, 45, 55 and $35/55^{\circ}C$. The storage stability and the development of browning by oxidative rancidity were also discussed. Monolayer coverage value of water content in dried file-fish was $8.03\%$ at $0.21\;a_w$Lipid oxidation at $35^{\circ}C$ was developed with increasing water activity but at $45^{\circ}C$and $55^{\circ}C$ it was rapidly progressed without clear differences between water activities except $0.44\;a_w$. The rate of reaction was more sensitive to storage temperature than to water activity. Browning in methanol-chloroform fraction was developed linearly by the progress of lipid oxidation which suggested that lipid oxidation was greatly influential to the development of browning in dried fish meat. In kinetical analysis the oxidation followed a zero order reaction mechanism as a function of carbonyl value. The activation energies obtained from the Arrhenius plot ranged 9.0 to 10.8 Kcal/mol and $Q_10$ values, 1.6-1.7. Shelf-lives at the storage of 35,45 and $55^{\circ}C$ ranged 58 days to 8 days. And in the fluctuating temperature storage at $35/55^{\circ}C$, shelf-lives were 17, 16, 15 and 13 days at 0.44, 0.52, 0.65 and $0.75\;a_w$, respectively. The shelf-lives for assessed from the accelerated shelf-life test were 125, 123, 120 and 106 days at 0.44, 0.52, 0.65 and $0.75\;a_w$, respectively, in the case of storage at $25^{\circ}C$.

• Applied Chemistry for Engineering
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• v.25 no.5
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• pp.515-519
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• 2014

The fuel properties of biodiesel produced by changing the mixing ratio of methanol and ethanol in trans-esterification of soybean oil and lard were evaluated in this paper. The solubility of oil and fat in ethanol was higher than that in methanol. Also the more homogeneous biodiesel was produced as increasing the mole ratio of ethanol. The conversion characteristics of lard was the best at the mixing mole ratio of methanol and ethanol was 6 : 6 at the reaction temperature of $60^{\circ}C$. On the other hands, the best biodiesel conversion characteristics for soybean oil was obtained at the mixing mole ratio of 3 : 3. The kinematic viscosities of soybean oil and lard based biodiesel were 4.17~4.35 cSt and 4.69~4.93 cSt, respectively. The oxidation stability and higher heating value increased with increasing the mole ratio of ethanol. The oxidation stability satisfied the criteria of biodiesel quality of 6 hours. And finally, the higher heating value was approximately 40 MJ/kg.