• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.629-633
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• 1998

The synthesis of 1,1-difluoroethane from acetylene as a function of HF/acetylene ratio, contact time and reaction temperature was studied on a fluorinated ${\gamma}-Al_2O_3$. The fluorination of ${\gamma}-Al_2O_3$ was treated with pure HF gas at high temperature. The crystallinity, the porosity, and the acid properties of the prepared samples were examined using XRD, the nitrogen adsorption, pyridine-IR and ammonia-TPD respectively. The activity was enhanced by further fluorination of alumina. The fraction of 1,1-difluoroethane was obtained above 90% at reaction temperature of about $200^{\circ}C$. The ratio of 1,1-difluoroethane to vinylfluoride over fluorinated ${\gamma}-Al_2O_3$ catalyst was increased with the mole ratio of HF/acetylene and contact time, and was found to be the highest ratio at reaction temperature of $200^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.18 no.8
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• pp.831-840
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• 1997

Core/shell structured composite metal oxides of Fe2O3/MgO were prepared by thermal decomposition of Fe(acac)3 adsorbed on the surface of MgO cores. The morphology of the composites conformed to that of the MgO used as the cores. Broad powder X-ray diffraction peaks shifted toward larger d, large BET surface area (∼350 m2/g), and the size of crystalline domains in nano range (4 nm), all corroborate to the nanocrystallinity of the Fe2O3/MgO composite which was prepared by using nanocrystalline MgO as the core. By use of microcrystalline MgO as the core, microcrystalline Fe2O3/MgO composite was prepared, and it had small BET surface area of less than 35 m2/g. AFM measurements on nanocrystalline Fe2O3/MgO showed a collection of spherical aggregates (∼80 nm dia) with a very rough surface. On the contrary, microcrystalline Fe2O3/MgO was a collection of plate-like flat crystallites with a smooth surface. The nitrogen adsorption-desorption behavior indicated that microcrystalline Fe2O3/MgO was nonporous, whereas nanocrystalline Fe2O3/MgO was mesoporous. Bimodal distribution of the pore size became unimodal as the layer of Fe2O3 was applied to nanocrystalline MgO. The macropores in a wide distribution which the nanocrystalline MgO had were absent in the nanocrystalline Fe2O3/MgO. The decomposition of CCl4 was largily enhanced by the overlayer of Fe2O3 on nanocrystalline MgO making the reaction between nanocrystalline Fe2O3/MgO and CCl4 be nearly stoichiometric. The reaction products were environmentally benign MgCl2 and CO2. Such an enhancement was not attainable with the microcrystalline samples. Even for the nanocrystalline MgO, the enhancement was not attained, if not with the Fe2O3 layer. Without the layer of Fe2O3, it was observed that the nanocrystalline domain of the MgO transformed into microcrystalline one as the decomposition of CCl4 proceeded on its surface. It appeared that the layer of Fe2O3 on the particles of nanocrystalline Fe2O3/MgO blocked the transformation of the nanocrystalline domain into microcrystalline one. Therefore, in order to attain stoichiometric reaction between CCl4 and Fe2O3/MgO core/shell structured composite metal oxide, the morphology of the core MgO has to be nanocrystalline, and also the nanocrystalline domains has to be sustained until the core was exhausted into MgCl2.

• Journal of Soil and Groundwater Environment
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• v.21 no.1
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• pp.28-39
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• 2016

Struvite (MgNH₄PO₄ ⋅ 6H₂O) and hydroxyapatite (HAP, Ca₁₀(PO₄)₆(OH)₂) precipitation in urine-separating toilets (NoMix toilets) causes severe maintenance problems and also reduce the phosphate and calcium content. Application of urine separating technique and extraction of by-products from human urine is a cost effective technique in waste water treatment. In this study, we extract urine calcite from human urine by batch scale method, using urease producing microbes to trigger the precipitation and calcite formation process. Extracted urine calcite (calcining at 800℃) is a potential adsorbent for removal of heavy metal(loid)s like (Cd²⁺, Cu²⁺, Ni²⁺, Pb²⁺, Zn²⁺ and As³⁺) along with additional leaching analysis of total nitrogen (T-N), phosphate (T-P) and chemical oxygen demand (COD). The transformations of calcite during synthesis were confirm by characterization using XRD, SEM-EDAX and FT-IR techniques. In additional, the phosphate leaching potential and adsorbate (nitrate) efficiency in aqueous solution was investigated using the calcinedurine calcite. The results indicate that the calcite was effectively remove heavy metal(loid)s lead up to 96.8%. In addition, the adsorption capacity (q_e) of calcite was calculated and it was found to be 203.64 Pb, 110.96 Cd, 96.02 Zn, 104.2 As, 149.54 Cu and 162.68 Ni mg/g, respectively. Hence, we suggest that the calcite obtain from the human urine will be a suitable absorbent for heavy metal(loid)s removal from aqueous solution.

• Clean Technology
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• v.27 no.3
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• pp.223-231
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• 2021

In order to address many issues associated with large volume changes of silicon, which has very low electrical conductivity but offers about 10 times higher theoretical capacity than graphite (Gr), a silicon nanoparticles/hollow carbon (SiNP/HC) composite having bimodal-mesopores was prepared using silica nanoparticles as a template. A control SiNP/C composite without a hollow structure was also prepared for comparison. The physico-chemical and electrochemical properties of SiNP/HC were analyzed by X-ray diffractometry, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements for surface area and pore size distribution, scanning electron microscopy, transmission electron microscopy, galvanostatic cycling, and cyclic voltammetry tests to compare them with those of the SiNP/C composite. The SiNP/HC composite showed significantly better cycle life and efficiency than the SiNP/C, with minimal increase in electrode thickness after long cycles. A hybrid composite, SiNP/HC@Gr, prepared by physical mixing of the SiNP/HC and Gr at a 50:50 weight ratio, exhibited even better cycle life and efficiency than the SiNP/HC at low capacity. Thus, silicon/carbon composites designed to have hollow spaces capable of accommodating volume expansion were found to be highly effective for long cycle life of silicon-based composites. However, further study is required to improve the low initial coulombic efficiency of SiNP/HC and SiNP/HC@Gr, which is possibly because of their high surface area causing excessive electrolyte decomposition for the formation of solid-electrolyte-interface layers.

• Applied Chemistry for Engineering
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• v.32 no.6
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• pp.621-626
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• 2021

A sequential design of experiments was used to optimize MOF-801 synthesis process. For the initial screening, a general 2^k factorial design was selected followed by the central composition design, one of the response surface methods. A 2³ factorial design based on the molar ratio of fumaric acid, dimethylformamide (DMF), and formic acid was performed to select the more suitable response variable for the design of experimental method among the crystallinity and BET specific surface area of MOF-801. After performing 8 synthesis experiments designed by MINITAB 19 software, the characteristic analysis was performed using XRD analysis and nitrogen adsorption method. The crystallinity with R² = 0.999 was found to be more suitable for the experimental method than that of BET specific surface area. Based on analysis of variance (ANOVA), it was confirmed that the molar ratio of fumaric acid and formic acid was a major factor in determining the crystallinity of MOF-801. Through the response optimization and contour plot of two factors, the optimal molar ratio of ZrOCl₂·8H₂O : fumaric acid : DMF : formic acid was 1 : 1 : 39 : 35. In order to optimize the synthesis process, the central composition design on synthesis time and temperature was performed under the identical molar ratio of precursors. The results derived through the designed 9 synthesis experiments were calculated using the quadratic model equation. Thus, the maximum crystallinity of MOF-801 predicted under the synthesis time and temperature of 7.8 h and 123 ℃, respectively.

• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.714-722
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• 2019

Catalysts were prepared by using incipient wetness impregnation method with 17 wt% Ni on a support ($SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, $SiO_2$, $TiO_2$, MgO) and the catalytic activity in the reductive amination of ethanol with ammonia in the presence of hydrogen was compared and evaluated. The catalysts used before and after the reaction were characterized using X-ray diffraction, nitrogen adsorption, ethanol-temperature programmed desorption (EtOH-TPD), isopropanol-temperature programmed desorption (IPA-TPD), and hydrogen chemisorption etc. In the case of preparing $ZrO_2$ and $Y_2O_3$ supports, the small amount of Si dissolution from the Pyrex reactor surface provoked the formation of mixed oxides $SiO_2-ZrO_2$ and $SiO_2-Y_2O_3$. Among the catalysts used, $Ni/SiO_2-Y_2O_3$ catalyst showed the best activity, and this good activity was closely related to the highest nickel dispersion, and low desorption temperature in EtOH-TPD and IPA-TPD. The low catalytic activity on Ni/MgO catalysts showed low activity due to the formation of NiO-MgO solid-solutions. In the case of $Ni/TiO_2$, the reactivity was low due to the low nickel metal phase due to strong metal-support interaction. In the case of using a support as $SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, and $SiO_2$, the selectivities of ethylamines and acetonitrile were not significantly different at similar ethanol conversion.

• Korean Chemical Engineering Research
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• v.57 no.1
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• pp.133-141
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• 2019

High specific surface area zirconia with acid-basic property was synthesized by precipitation using reflux method or hydrothermal synthesis method using ammonium hydroxide solution as precipitant in the range of pH of Zr solution from 2 to 10. The prepared zirconia was characterized by the nitrogen adsorption, X-ray diffraction (XRD), isopropanol temperature programmed desorption (IPA-TPD), scanning electron microscopy and X-ray photoelectron spectroscopy, and the catalytic activity in the IPA decomposition reaction was correlated with the acid-basic properties. When using reflux method, high pH of Zr solution was required to obtain high fraction of tetragonal zirconia, and pure tetragonal zirconia was possible at pH 9 or higher. High pH was required to obtain high specific surface area zirconia, and the hydrous zirconia synthesized at pH 10 had high specific surface area zirconia of $260m^2g^{-1}$ even after calcination at $600^{\circ}C$. However, hydrothermal synthesis with high pressure under the same conditions resulted in very low specific surface area below $40m^2g^{-1}$ and monoclinic phase zirconia was synthesized. High pH of the solution was required to obtain high specific surface area tetragonal phase zirconia. In hydrothermal synthesis requiring high pressure, monoclinic zirconia was produced irrespective of the pH of the solution, and the specific surface area was relatively low. Zirconia with high specific surface area and tetragonal phase was predominantly acidic compared to basicity and only propylene, which was observed as selective dehydration reaction in IPA decomposition reaction, was produced.

• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.611-619
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• 2019

This study was carried out to investigate fuel decomposition characteristics and coke formation according to types of endothermic fuels and methods of catalyst molding. Methylcyclohexane (MCH), n-dodecane, and exo-tetrahydrodipentadiene (exo-THDCP) were used as the endothermic fuels. As a catalyst, USY720 supported with platinum was used. It was manufactured by only using pressure to disk-type, or pelletized with a binder and a silica solution. The characteristics of the catalysts according to the molding method were analyzed by X-ray diffraction analysis, scanning electron microscopy, nitrogen adsorption-desorption isotherm, and ammonia temperature programmed desorption analysis. The reaction was carried out under conditions of high temperature and high pressure ($500^{\circ}C$, 50 bar) in which the fuel could exist in a supercritical state. The product was analyzed by gas chromatograph/mass spectrometer and the coke produced by the catalyst was analyzed by thermogravimetric analyzer. After the reaction, the composition of the products varied greatly depending on the structure of the fuel. In addition, the crystallinity and surface properties of the catalysts were not changed by the method of catalyst molding, but the changes of the acid sites and the pore characteristics were observed, which resulted in changes in the amount and composition of products and coke.

• Applied Chemistry for Engineering
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• v.32 no.1
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• pp.83-90
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• 2021

In this study, effects of the physical and chemical properties of low temperature heated carbon on electrochemical behavior as a secondary battery anode material were investigated. A heat treatment at 600 ℃ was performed for coking of petroleum based pitch, and the manufactured coke was heat treated with different heat temperatures at 700~1,500 ℃ to prepare low temperature heated anode materials. The physical and chemical properties of carbon anode materials were studied through nitrogen adsorption and desorption, X-ray diffraction (XRD), Raman spectroscopy, elemental analysis. Also the anode properties of low temperature heated carbon were considered through electrochemical properties such as capacity, initial Coulomb efficiency (ICE), rate capability, and cycle performance. The crystal structure of low temperature (≤ 1500 ℃) heated carbon was improved by increasing the crystal size and true density, while the specific surface area decreased. Electrochemical properties of the anode material were changed with respect to the physical and chemical properties of low temperature heated carbon. The capacity and cycle performance were most affected by H/C atomic ratio. Also, the ICE was influenced by the specific surface area, whereas the rate performance was most affected by true density.

• Applied Chemistry for Engineering
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• v.33 no.6
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• pp.600-605
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• 2022

In this study, nitrogen oxide (NO_x) removal experiments were performed using a graphene based ceramic filter coated with a V₂O₅-WO₃-TiO₂ catalyst. Graphene oxide (GO) was prepared by Hummer's method using graphite, and the reduced graphene oxide was produced by reducing with hydrazine (N₂H₄). Vanadium (V), Tungsten (W), and Titanium (Ti) were coated by the sol-gel method, and then a metal oxide-supported filter was prepared through a calcination process at 350 ℃. A NO_x removal efficiency test was performed for the catalytic ceramic filters with UV light in a humid condition. When graphene oxide (GO) and reduced graphene oxide (rGO) were present on the filter, the NOx removal efficiency was superior to that of the conventional ceramic filter. Most likely, this is due to an improvement in the adsorption properties of NOx molecules on graphene coated surfaces. As the concentration of graphene increased, higher NO_x removal efficiency was confirmed.