• Journal of the Korean Chemical Society
• /
• v.31 no.2
• /
• pp.197-202
• /
• 1987

Sigmatropic rearrangement of cis and trans-2-methyl-N-phenyl-1,3-oxathiolane-2-acetamide (b) and (c) gave unisolable sulfenic acids (d) and (f), respectively. These sulfenic acids were confirmed by deuterium exchange reactions involving 2-methylene and 2-methyl groups. The reactions also showed that no isomerization between the cis and trans sulfoxides (b) and (c) occurred under neutral conditions. However, the isomerization took place in the presence of acid catalyst. Stereospecific recyclization of sulfenic acids to the sulfoxides is attributable to possible hydrogen bonding between sulfenyl oxygen and NH proton or it arises from the geometrical requirements of the reacting bond and atoms in the reverse sigmatropic rearrangement. In the oxidation of 1, 3-oxathiolane, cis sulfoxide (b) could be obtained selectively in high yield by using $H_2O_2$-benzene seleninic acid.

• Korean Chemical Engineering Research
• /
• v.52 no.6
• /
• pp.695-700
• /
• 2014

Proton Exchange Membrane Fuel Cells (PEMFC) can generate hydrogen and oxygen from water by electrolysis. But the electrode and polymer electrolyte membrane degrade rapidly during PEM water electrolysis because of high operation voltage over 1.7V. In order to reduce the rate of anode electrode degradation, unsupported $IrO_2$ catalyst was used generally. In this study, Pt/C catalyst for PEMFC was used as a water electrolysis catalyst, and then the degradation of catalyst and membrane were analysed. After water electrolysis reaction in the voltage range from 1.8V to 2.0V, I-V curves, impedance spectra, cyclic voltammograms and linear sweep voltammetry (LSV) were measured at PEMFC operation condition. The degradation rate of electrode and membrane increased as the voltage of water electrolysis increased. The hydrogen yield was 88 % during water electrolysis for 1 min at 2.0V, the performance at 0.6V decreased to 49% due to degradation of membrane and electrode assembly.

• YAKHAK HOEJI
• /
• v.38 no.4
• /
• pp.455-461
• /
• 1994

Each nitrogen and oxygen site isotope enriched the cyclophosphamide metabolite phosphoramide mustard was synthesized. Reaction of N,N-bis(2-chloroethyl)phosphoramidic dichloride$[Cl_2P(O)N(CH_2CH_2Cl)_2]$ with benzyl alcohol and ammonia gave N,N-bis(2-chloroethyl)phosphorodiamidic acid phenylmethyl ester $[BzO(H_2N)P(O)N(CH_2CH_2Cl)_2]$. Catalytic hydrogenation of this benzyl ester followed by the addition of cyclohexylamine provided PM. Incorporation of $^{15}NH_3$ into this general scheme gave PM with a $^{15}NH_2$ moiety. Glycine-$^{15}N$ was converted to bis(2-chloroethyl)amine-$^{15}N$ hydrochloride which, in turn, provided for N,N-bis(2-chloroethyl)phosphorodiamidic-$^{15}N$ dichloride. Use of this compound in the general synthetic pathway yielded PM CHA with $^{15}N$ in the mustard moiety. $^{17}O$-Enriched PM was generated through the use of benzyl alcohol-$^{17}O$. To obtain the alcohol, labelled benzaldehyde was made by exchange with $^{17}OH_2$ and was then reduced with sodium borohydride.

• 한국연소학회:학술대회논문집
• /
• 2002.11a
• /
• pp.237-240
• /
• 2002

Micro catalytic reactors are alternative propulsion device that can be used on a nano satellite. When used with a monopropellant, $H_2O_2$, a micro catalytic reactor needs only one supply system as the monopropellant reacts spontaneously on contact with catalyst and releases heat without external ignition, while separate supply lines for fuel and oxidizer are needed for a bipropellant rocket engine. Additionally, $H_2O_2$ is in liquid phase at room temperature, eliminating the burden of storage for gaseous fuel and carburetion of liquid fuel. In order to design a micro catalytic reactor, an appropriate catalyst material must be selected. Considering the safety concern in handling the monopropellants and reaction performance of catalyst, we selected hydrogen peroxide at volume concentration of 70% and perovskite redox catalyst of lantanium cobaltate doped with strondium. Perovskite catalysts are known to have superior reactivity in reduction-oxidation chemical processes. In particular, lantanium cobaltate has better performance in chemical reactions involving oxygen atom exchange than other perovskite materials. In the present study, a process to prepare perovskite type catalyst, $La_{0.8}Sr_{0.2}CoO_3$, and measurement of its propellant decomposition performance in a test reactor are described.

• Transactions of the Korean hydrogen and new energy society
• /
• v.27 no.2
• /
• pp.155-162
• /
• 2016

A proton exchange membrane fuel cell (PEMFC) produces only water at cathode by an electrochemical reaction between hydrogen and oxygen. The generated water is transported across the membrane from the cathode to the anode. The transported water collected in water-trap and drained to the cathode within the humidifier outlet. If the condensate water is not being drained at the appropriate time, condensate water in the anode can cause the performance degradation or fuel efficiency degradation of fuel cell by the anode flooding or unnecessary hydrogen discharge. In this study, we proposed an optimization method of condensate water drain logic for the water drain performance and the water drain algorithm as considered the condensate water generating speed prep emergency case. In conclusion, we developed the water management strategy of fuel processing system (FPS) as securing fuel efficiency and operating stability.

• Bulletin of the Korean Chemical Society
• /
• v.21 no.3
• /
• pp.305-309
• /
• 2000

The cerium ion intercalated aluminosilicate was prepared by ion exchange reaction between $Na^+$ in montmorillonite and $Ce^{+4}$ in aqueous solution. The X-ray absorption near edge structrure(XANES) analyses indicate that the $Ce^{+4}$ ions are partially reduced to the $Ce^{+3}$ ones during the intercalation into layered aluminosilicate due to a charge transfer between host and intercalant. From the EXAFS analysis, two different (Ce-O) bonding pairs could be characterized with the distances and coordination numbers of 2.31 $({\pm}0.02){\AA}$ ${\times}$ 8.2 $({\pm}1.5)$ and 2.66 $({\pm}0.02){\AA}$ ${\times}$ 2.7 $({\pm}1.0)$, respectively, with the oxygen atoms as the first nearest neighbor, and two (Ce-Ce) pairs at 3.78 ${\AA}$ as the second neighbor. It is therefore concluded that the most probable Ce-species stabilized in the interlayer space of aluminosilicate after the intercalation is the tetrameric Ce-polyoxy/hydorxy cations with the mixed valent state of 0.75 $Ce^{+4}$.0.25 $Ce^{+3}$.

• Korean Journal of Materials Research
• /
• v.30 no.5
• /
• pp.267-271
• /
• 2020

Cerium oxide (ceria, CeO₂) is one of the most wide-spread oxide supporting materials for the precious metal nanoparticle class of heterogeneous catalysts. Because ceria can store and release oxygen ions, it is an essential catalytic component for various oxidation reactions such as CO oxidation (2CO + O₂ 2CO₂). Moreover, reduced ceria is known to be reactive for water activation, which is a critical step for activation of water-gas shift reaction (CO + H₂O → H₂ + CO₂). Here, we apply van der Waals-corrected density functional theory (DFT) calculations combined with U correction to study the mechanism of water chemisorption on CeO₂(111) surfaces. A stoichiometric CeO₂(111) and a defected CeO₂(111) surface showed different water adsorption chemistry, suggesting that defected CeO₂ surfaces with oxygen vacancies are responsible for water binding and activation. An appropriate level of water-ceria chemisorption energy is deduced by vdW-corrected non-local correlation coupled with the optB86b exchange functional, whereas the conventional PBE functional describes weaker water-ceria interactions, which are insufficient to stabilize (chemisorb) water on the ceria surfaces.

• Journal of the Korean Applied Science and Technology
• /
• v.17 no.1
• /
• pp.1-5
• /
• 2000

The selective catalytic reduction(SCR) of nitric oxide by ethane in the presence of oxygen was investigated on Cu-ZSM-5, Co-ZSM-5 and Ga-ZSM-5 catalysts over a range of 400, 450 and $500^{\circ}C$. The catalysts were prepared by ion-exchange method. The composition of the reactant gases were 1000 ppm of NO, 1000 ppm of $C_{2}H_{6}$ and 2.5% of $O_{2}$, and the reaction was conducted in a fixed-bed reactor at 1 atm. For the 20wt% Co-ZSM-5(50) catalyst, the NO conversion reached up to 100%, while the $C_2H_6$ conversion and the CO selectivity were about 50% and 25%, respectively, at $450^{\circ}C$. For the 20wt% Cu-ZSM-5(50) catalyst, the NO conversion and the C2H6 conversion were about 80% and 100%, respectively, but there was no CO produced. The metal ion-exchanged ZSM-5 catalysts exhibited a tendency to increase the NO conversion with the Si/Al ratio of the ZSM-5, that is, NO conversion was inversely proportional to the acidity of the catalysts. But, the effect of the acidity on NO conversion was not so large. From the XRD results of the catalysts before and after SCR reaction it was found that there was no structural change.

• Clean Technology
• /
• v.19 no.3
• /
• pp.287-294
• /
• 2013

The $NH_3$-selective catalytic reduction (SCR) reaction of NO with excess of oxygen were systematically investigated over Cu-zeolite and Fe-zeolite catalysts. Cu-zeolite and Fe-zeolite catatysts to adapt the SCR technology for mobile diesel engines were prepared by liquid ion exchange and incipient wetness impregnation of $NH_4$-BEA and $NH_4$-ZSM-5 zeolites. The catalysts were characterized by BET, XRD, FE-TEM (field emission transmission electron microscopy) and SEM/EDS. The SCR examinations performed under stationary conditions showed that the Cu-exchanged BEA catalyst revealed pronounced performance at low temperatures of $200{\sim}250^{\circ}C$. With respect to the Fe-zeolite catalyst, the Cu-zeolite catalyst showed a higher activity in the SCR reaction at low temperatures below $250^{\circ}C$. BEA zeolite based catalyst exhibited good activity in comparison with ZSM-5 zeolite based catalyst at low temperatures below $250^{\circ}C$.

• Applied Chemistry for Engineering
• /
• v.25 no.1
• /
• pp.78-83
• /
• 2014

In this research, we evaluated the performance and characteristics of carbon supported PtM (M = Ni and Y) alloy catalysts (PtM/Cs) synthesized by a modified polyol method. With the PtM/Cs employed as a catalyst for the oxygen reduction reaction (ORR) of cathodes in proton exchange membrane fuel cells (PEMFCs), their catalytic and ORR activities and electrical performance were investigated and compared with those of commercial Pt/C. Their particle sizes, particle distributions and electrochemically active surface areas (EAS) were measured by TEM and cyclic voltammetry (CV), while their ORR activity and electrical performance were explored using linear sweeping voltammetries with rotating disk electrodes and rotating ring-disk electrodes as well as PEMFC single cell tests. TEM and CV measurements show that PtM/Cs have the compatible particle size and EAS with Pt/C. When it comes to ORR activity, PtM/C showed the equivalent or better half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production(%) to or than commerical Pt/C. Based on results gained by the three electrode tests, when the PEMFC single cell tests were carried out, the current density measured at 0.6 V and maximum power density of PEMFC single cell adopting PtM/C catalysts were better than those adopting Pt/C catalyst. It is therefore concluded that PtM/C catalysts synthesized by modified polyol can result in the equivalent or better ORR catalytic capability and PEMFC performance to or than commercial Pt/C catalyst.