• Applied Biological Chemistry
• /
• v.37 no.3
• /
• pp.210-215
• /
• 1994

${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-phenyl\;phosphorothiolate-^{18}O$ and other related compounds were prepared and oxidized with m-chloroperbenzoic acid (MCPBA). Each reaction was followed by $^{31}P$ NMR and the products were analyzed by GC-MS. ${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-phenyl\;phosphorothiolate-^{18}O$ was converted to diethyl methyl phosphate in methanol by MCPBA and it was confirmed to contain $^{18}O$, which proved that the originally proposed mechanism of Segall and Casida operates in the oxidative reaction.

• Korean Journal of Fisheries and Aquatic Sciences
• /
• v.6 no.1_2
• /
• pp.37-43
• /
• 1973

In this paper, non-enzymatic browning reactions as a factor of self stability of boiled and dried anchovy were studied to discuss the effect of water activity to the discoloring reaction and the preservative moisture content. The development of rancidity of the fish meat was also mentioned since the fish is fatty and the lipid oxidation is a functional deteriorative reaction. Fresh anchovies were boiled in $10\%$ salt solution immediately after the catch, sun dried, and stored at room temperature ($20^{\circ}C$) for two months in humidistat chambers maintaining different levels of water activity as described in Table 1. The pigments formed by non-enzymatic browning reations were extracted in two fractions, those were chloroform-methanol soluble and water dialyzed fraction, and analyzed spectrophotometrically at the wavelength of 460 nm. These two fractions were considered, respectively to be the brown pigments formed by lipid oxidation reactions for the formler and for the latter, to be the pigments developed by sugar-amino or Maillard reaction. The oxidation of lipid in anchovy meat during the storage was measured as the changes in Peroxide value and the color development of thiobarbituric acid reaction. It is summarized from the results that the rate of both reactions, lipid oxidation and browning, was affected by water activity levels. In regard to the changes in peroxide and TBA value during the storage, the propagation of lipid oxidation was obviously accelerated at lower humidities whereas the development of browning progressed at the higher. These two reactions occurring simultaneously and contrary in activity resulted in that the rate of deterioration occurring oxidatively or by browning, was the minimum at the water activity of 0.32-0.45 which were $7-9\%$ as moisture content and slightly higher value than that of monolayer (Aw=0.21, $5.11\%$ as moisture content). It is also noted that the lipid oxidative browning was presumed to dominate sugar-amino reactions so that the rate of browning of the meat was ultimately depended on the development of rancidity although sugar-amino reactions initiated earlier than the other at the first ten days of storage, particulary at higher humidity. At the lower humidity sugar-amino reactions were occurred gradually but lower levels in color development in contrast to the consistent increase in lipid oxidative browning.

• Journal of Electrochemical Science and Technology
• /
• v.15 no.1
• /
• pp.67-95
• /
• 2024

Direct alcohol fuel cells (DAFCs) have gained much attention as promising energy conversion devices due to their ability to utilize alcohol as a fuel source. In this regard, Molybdenum-based electrocatalysts (Mo-ECs) have emerged as a substitution for expensive Pt and Ru-based co-catalyst electrode materials in DAFCs, owing to their unique electrochemical properties useful for alcohol oxidation. The catalytic activity of Mo-ECs displays an increase in alcohol oxidation current density by several folds to 1000-2000 mA mg_Pt^-1, compared to commercial Pt and PtRu catalysts of 10-100 mA mg_Pt^-1. In addition, the methanol oxidation peak and onset potential have been significantly reduced by 100-200 mV and 0.5-0.6 V, respectively. The performance of Mo-ECs in both acidic and alkaline media has shown the potential to significantly reduce the Pt loading. This review aims to provide a comprehensive overview of the bifunctional mechanism involved in the oxidation of alcohols and factors affecting the electrocatalytic oxidation of alcohol, such as synthesis method, structural properties, and catalytic support materials. Furthermore, the challenges and prospects of Mo-ECs for DAFCs anode materials are discussed. This in-depth review serves as valuable insight toward enhancing the performance and efficiency of DAFC by employing Mo-ECs.

• 한국신재생에너지학회:학술대회논문집
• /
• 2006.11a
• /
• pp.316-319
• /
• 2006

There is a worldwide interest in the development and commercialization of Polymer Electrolyte Membrane Fuel Cells (PEMFCs) for vehicular and stationary applications. One of the major objectives is the reduction of loaded electrode materials, which is comprise of the Pt-based noble metals. In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the deposition of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled active materials were formed on the surface of carbon-supported Au nanoparticles. The structural and electrochemical analyses indicate that the active materials were deposited on the surface of Au nanoparticles selectively and that an at toying process occurred during the successive reducing process The carbon-supported & surface-alloys showed the higher electrocatalytic activity than those of the particle-alloys and commercial one (Johnson-Matthey) for the reaction of methanol and formic acid oxidation. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.

• New & Renewable Energy
• /
• v.2 no.4 s.8
• /
• pp.64-69
• /
• 2006

There is a worldwide interest in the development and commercialization of polymer electrolyte membrane fuel cells [PEMFCs] for vehicular and stationary applications. One of the major objectives is the reduction of loaded electrode materials, which is comprise of the Pt-based noble metals. In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the supporting of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled active materials were formed on the surface of carbon-supported Au nanoparticles. The structural and electrochemical analyses indicate that the active materials were deposited on the surface of Au nanoparticles selectively and that an alloying process occurred during the successive reducing process. The carbon-supported & surface-alloys showed the higher electrocatalytic activity than those of the particle-alloys and commercial one [Johnson-Matthey] for the reaction of methanol and formic acid oxidation. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.

• Journal of Electrochemical Science and Technology
• /
• v.11 no.3
• /
• pp.273-281
• /
• 2020

Constructing and making highly active and stable nanostructured Pt-based catalysts with ultralow Pt loading are still electrifying for electrochemical applications such as water electrolysis and fuel cells. In this study, MoO₃ ribbons (RBs) of few micrometer in length is successfully synthesized via hydrothermal synthesis. Subsequently, 3-dimentional (3D)-silicate layer for about 10 to 15 nm is introduced via chemical deposition onto the pre-formed MoO₃ RBs; to setup the platform for Pt metaldots (MDs) deposition. In comparison with the bare MoO₃ RBs, the MoO₃-Si has served as a efficient solid-support for stabilizing and accommodating the uniform deposition of sub-2 nm Pt MDs. Such a structural design would effectively assist in improving the electronic conductivity of a fabricated MoO₃-Si-Pt catalyst towards MOR; the interfaced, porous and 3D silicate layer has assisted in an efficient mass transport and quenching the poisonous CO_ads species leading to a significant electrocatalytic performance for MOR in alkaline medium. Uniformly decorated, sub-2 nm sized Pt MDs has synergistically oxidized the MeOH in association with the MoO₃-Si solid-support hence, synergistic catalytic activity has been achieved. Present facile approach can be extended for fabricating variety of highly efficient Metal Oxide-Metal Nanocomposite for energy harvesting applications.

• 한국신재생에너지학회:학술대회논문집
• /
• 2005.06a
• /
• pp.227-230
• /
• 2005

There is a worldwide interest In the development and commercialization of PEMFCs for vehicular and stationary applications. The major problem in the practical use of PEMFCs is the deactivation of the Pt anode electrocatalyst by the adsorption of carbon monoxide. Therefore, intensive work has been devoted to finding electrocatalysts that are tolerant to CO in hydrogen at operating temperatures bellow $100^{\circ}C$. Also, DMFC is considered to be one of the most promising technologies for energy generation. But, the most important problem associated with the DMFC is the slow reaction rate of methanol oxidation and the second major problem is fuel crossover. So, the performance of a state-of-the-art DMFC is considerably lower than that of hydrogen-fuelled PEMFC. In this research, the preparation and characterization of electrode materials will be introduced. Also, some electrochemical techniques for the characterization of PEMFCs will be presented.

• Journal of environmental and Sanitary engineering
• /
• v.15 no.4
• /
• pp.44-51
• /
• 2000

The reactivity of a range of volatile organic compounds with differing functional groups observed over 0.5% $Pt/{\gamma}-Al_2O_3$ catalyst. In general, the reactivity pattern observed was alcohols > aromatics > ketones > cycloalkane > alkanes. The deep conversion was increased as reaction temperature was increased. A correlation was found between the reactivity of the individual and the strength of the weakest C-Hbond in structure. The conversion of volatile organic compounds increases in order methanol > benzene > cyclohexane > MEK > n-hexane. That is the effect of differences in total dissociation energy. An apparent zeroth-order kinetics with respect to inlet concentration have been observed. A simple multicomponent model based on two-stage redox model made reasonably good predictions of conversion over the range of parameters studied. thus, the catalytic process was suggested as the new VOCs control technology.

• Journal of the Korean Chemical Society
• /
• v.36 no.6
• /
• pp.894-905
• /
• 1992

Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$ $10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.

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