• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• Journal of Hydrogen and New Energy
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• v.25 no.4
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• pp.378-385
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• 2014

In this research, we investigate electrical performance and electrochemical properties of graphene supported Pt (Pt/G) and PtM (M = Ni and Y) alloy catalysts (PtM/Gs) that are synthesized by modified polyol method. With the PtM/Gs that are adopted for oxygen reduction reaction (ORR) as cathode of proton exchange membrane fuel cells (PEMFCs), their catalytic activity and ORR performance and electrical performance are estimated and compared with one another. Their particle size, particle distribution and electrochemically active surface (EAS) area are measured by TEM and cyclic voltammetry (CV), respectively. On the other hand, regarding ORR activity and electrical performance of the catalysts, (i) linear sweeping voltammetry by rotating disk electrode and rotating ring-disk electrode and (ii) PEMFC single cell tests are used. The TEM and CV measurements demonstrate particle size and EAS of PtM/Gs are compatible with those of Pt/G. In case of PtNi/G, its half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production % are excellent. Based on data obtained by half-cell test, when PEMFC singlecell tests are carried out, current density measured at 0.6V and maximum power density of the PEMFC single cell employing PtNi/G are better than those employing Pt/G. Conclusively, PtNi/Gs synthesized by modified polyol shows better ORR catalytic activity and PEMFC performance than other catalysts.

• Journal of the Korean Electrochemical Society
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• v.14 no.1
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• pp.50-55
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• 2011

To enhance the performance of a MEA (membrane electrode assembly) in a polymer electrolyte membrane fuel cell (PEMFC), optimum contents of Nafion ionomer as electrolyte in the 20 and 40 wt% Pt/C used in electrodes were examined. Variety characterization techniques were applied to examine optimum Nafion contents: cell performance test, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). According to Pt wt% supported on carbon support, it has been observed that polarization, ohmic, and mass transfer resistances were changed so that the cell performance was significantly dependent on the content of Nafion ionomer. Optimum Nafion ionomer contents in the 20 wt% Pt/C and 40 wt% Pt/C were showed 35 wt% and 20 wt%, respectively. This is due to different surface area of the Pt/C catalyst, and formation of triple phase boundary seems to be affected by the Nafion contents.

• Ceramist
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• v.23 no.2
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• pp.200-210
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• 2020

Supported catalysts are at the heart of manufacturing essential chemical, agricultural and pharmaceutical products. While the longevity of such systems is critically hinged on the durability of metal nanoparticles, the conventional deposition/dispersion techniques are difficult to enhance the stability of the metal nanoparticles due to the lack of control over the interaction between metal-support. Regarding this matter, ex-solution has begun to be recognized as one of the most promising methodologies to develop thermally and chemically robust nanoparticles. By dissolving desired catalysts as a cation form into a parent oxide, fine and uniformly distributed metal nano-catalysts can be subsequently grown in situ under reductive heat treatment, which is referred to ex-solution. Over the several years, ex-solved analog has resulted in tremendous progress in the chemical-electrochemical applications due to the exceptional robustness coupled with ease synthesis. Herein, we describe the ex-solution process in detail which therein introducing the unique characteristics of ex-solved particles that distinguish them from conventionally dispersed nanoparticles. We then go through the history of science regarding the ex-solution phenomena and summarize several major research achievements which embrace the ex-solved nanoparticles to markedly promote the catalytic performances. In conclusion, we address the remaining challenges and the future perspectives of this rapidly growing field.

• Journal of the Korean Institute of Gas
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• v.13 no.5
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• pp.26-32
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• 2009

Ni catalysts on mesoporous silica and commercial silica were prepared for the methanation. XRD and TPR analyses indicated that Ni/mesoporous silica had smaller metal particle size and higher metal dispersion than that of Ni/commercial silica. In addition, Ni/mesoporous silica had stronger metal-support interaction. In methanation, Ni/mesoporous silica showed higher CO conversion and methane yield (65%) than Ni/commercial silica (58%). In the characterization results of catalysts after reaction, Ni/commercial silica was deactivated by the collapse of structure and metal sintering, but Ni/mesoporous silica showed stable catalytic performance.

• Journal of the Korean Solar Energy Society
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• v.33 no.3
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• pp.42-50
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• 2013

Solar thermal reactor was studied for hydrogen production with a two step thermochemical cycle including T-R(Thermal Reduction) step and W-D(Water Decomposition) step. NiFe2O4 and Fe3O4 supported by monoclinic ZrO2 were used as a catalyst device and Ni powder was used for decreasing the T-R step reaction temperature. Maintaining a temperature level of about $1100^{\circ}C$ and $1400^{\circ}C$, for 2-step thermochemical reaction, is important for obtaining maximum performance of hydrogen production. The controller was designed for adjusting high temperature solar thermal energy heating the foam-device coated with nickel- ferrite powder. A Pill temperature control system was designed based on 2-step thermochemical reaction experiment data(measured concentrated solar radiation and the temperature of foam device during experiment). The cycle repeated 5 times, ferrite conversion rate are 4.49~29.97% and hydrogen production rate is 0.19~1.54mmol/g-ferrite. A temperature controller was designed for increasing the number of reaction cycles related with the amount of produced hydrogen.

• Journal of the Korean Wood Science and Technology
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• v.47 no.3
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• pp.344-359
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• 2019

Effects of various types of zeolite on the catalytic performance of hydrodeoxygenation (HDO) of bio-oil obtained from waste larch wood pyrolysis were investigated herein. Bifunctional catalysts were prepared via wet impregnation. The catalysts were characterized through XRD, BET, and SEM. Experimental results demonstrated that HDO enhanced the fuel properties of waste wood bio-oil, such as higher heating values (HHV) (20.4-28.3 MJ/kg) than bio-oil (13.7 MJ/kg). Water content (from 19.3 in bio-oil to 3.1-16.6 wt% in heavy oils), the total acid number (from 150 in bio-oil to 28-77 mg KOH/g oil in heavy oils), and viscosity (from 103 in bio-oil to $40-69mm^2/s$ in heavy oils) also improved post HDO. In our experiments, depending on the zeolite support, NiFe/HBeta exhibited a high Si/Al ratio of 38 with a high specific surface area ($545.1m^2/g$), and, based on the yield of heavy oil (18.3-18.9 wt%) and HHV (22.4-25.2 MJ/kg), its performance was not significantly affected by temperature and solvent concentration variations. In contrast, NiFe/zeolite Y, which had a low Si/Al ratio of 5.2, exhibited the highest improved quality for heavy oil at high temperature, with an HHV of 28.3 MJ/kg at $350^{\circ}C$ with 25 wt% of solvent.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.12
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• pp.2263-2273
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• 2000

Catalytic wet air oxidation of acetic acid over Mn-Ce based catalysts deposited on various supports ($SiO_2$, $TiO_2$, $ZrO_2$), $ZrSiO_4$, $ZrO_2(10wt%)/TiO_2$) have been carried out in high pressure microreactors. Also, promotional effects by small addition(O.5~1.0 wt%) of p-type semiconductors (CoO, $Ag_2O$, SnO) have been investigated. From the screening tests for initial activity ranking, both Mn(2.8)-Ce(7.2 wt%) and Ru(O.4)Mn(2.7)-Ce(6.9 wt%) supported on $TiO_2$ were selected as the promising reference candidates. In $Mn-Ce/TiO_2$ reference catalyst, addition of small amount of each p-type semiconductor (Co, Sn and Ag) resulted in activity promotional effect and the degree of the increase was in the following order: Co> Ag > Sn. Especially, $Mn-Ce/TiO_2$ promoted with 0.5 wt% Co gave the 2.6 folds activity increase compared to the reference case attributing to the surface area increase as well as synergy effect. In $Ru-Mn-Ce/TiO_2$ reference catalyst, only Co(1.0 wt%) promoted case showed a little reaction rate increase.

• Applied Chemistry for Engineering
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• v.10 no.4
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• pp.557-562
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• 1999

The reaction properties of Pd. Pd-Ce and Pd-La catalysts supported on ${\gamma}-Al_2O_3$ were investigated in the oxidation reaction of methane($CH_4$) exhausted from the compressed natural gas vehicle in a U-tube flow reactor with gas hourly space velocity of $72,000h^{-1}$. The catalysts were characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), BET surface area and hydrogen chemisorption. Pd catalyst prepared by $Pd(NO_3)_2$ as a palladium precursor and calcined at $600^{\circ}C$ showed the highest activity for a methane oxidation. Catalytic activity of calcined $Pd/{\gamma}-Al_2O_3$ in which most of palladium was converted into palladium oxide species was higher than that of reduced $Pd/{\gamma}-Al_2O_3$ in which most of palladium existed in palladium metal by XRD. As increasing the number of reaction cycles in the wide range of redox, the catalytic activity of $Pd/{\gamma}-Al_2O_3$ was decreased and the highly active window became narrower. Lanthanum oxide promoted Pd catalyst, $Pd/La/{\gamma}-Al_2O_3$ showed enhanced thermal stability compared with $Pd/{\gamma}-Al_2O_3$ even after aging at $1000^{\circ}C$, which was ascribed to the role of La as a promoter to suppress the sintering of palladium metal and ${\gamma}-Al_2O_3$ support. Almost all of methane was removed by the reaction with NO at the redox ratio of 1.2 in case of oxygen excluded steam, but that activity was significantly decreased in the steam containing oxygen.

• Journal of Energy Engineering
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• v.23 no.3
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• pp.157-162
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• 2014

In this research, we investigate electrical performance and electrochemical properties of carbon supported Pt (Pt/C) that is synthesized by polyol method. With the Polyol_Pt/C that is adopted for oxygen reduction reaction (ORR) as cathode of proton exchange membrane fuel cells (PEMFCs), their catalytic activity and ORR performance and electrical performance are estimated and compared with commercial Pt/C(Johnson Mattey) catalyst. Their electrochemically active surface (EAS) area are measured by cyclic voltammetry (CV), respectively. On the other hand, regarding ORR activity and electrical performance of the catalysts, (i) linear sweeping voltammetry by rotating disk electrode and (ii) PEMFC single cell tests are used. The CV measurement demonstrate EAS of Polyol_Pt/C is compared with commercial JM_Pt/C. In case of Polyol_Pt/C, its half-wave potential, kinetic current density are excellent. Based on data obtained by half-cell test, when PEMFC single cell tests are carried out, current density measured at 0.6V and maximum power density of the PEMFC single cell employing Polyol_Pt/C are better than those employing commercial Pt/C. Conclusively, Polyol_Pt/C synthesized by modified polyol process shows better ORR catalytic activity and PEMFC performance than other catalysts.