• Bulletin of the Korean Chemical Society
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• 제25권9호
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• pp.1379-1384
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• 2004

Rearrangements of 1,3-oxathiolane sulfoxides 8 and 9 in the presence of base are described from a mechanistic viewpoint of sigmatropic and elimination reactions. In the presence of triethylamine the (Z)-sulfoxide 8 gave the corresponding thiolsulfinate 10 by way of dimerization of the sulfenic acid intermediate 2 at room temperature while the (E)-sulfoxide 9 was recovered even after refluxing in ethyl acetate by the reversal of the [2,3]-sigmatropic rearrangement of the sulfenic acid 4. Triethylamine promoted the developing charge separation in the transition state of the sigmatropic rearrangement of the (Z)-sulfoxide 8 to facilitate the ring opening to the sulfenic acid 2. The reason for more facile ring opening of the (Z)-sulfoxide 8 in comparison with the corresponding (E)-sulfoxide 9 is attributable to the differences in the reactivity of the hydrogen adjacent to the carbonyl group. Triethylamine was not strong base to deprotonate the carbonyl-activated methylene hydrogen of the (E)-sulfoxide 9 but enough to catalyze the sigmatropic process of the sulfoxides. The sulfenic acid 2 dimerized to the thiolsulfinate 10 while the sulfenic acid 4 proceeded the sigmatropic ring closure. In the presence of strong base such as potassium hydroxide, the elimination reaction was predominant over the sigmatropic rearrangement. In this reaction condition, both sulfoxides 8a and 9a gave a mixture of the disulfide 12, the isomeric disulfide 14, and the sulfinic acid 13. Under the strong alkaline condition an elimination of activated hydrogen from the carbon adjacent to the carbonyl group to furnish the sulfenic acid 2a and the isomeric sulfenic acid 18. The formation of the transient intermediate in the reaction was proven by isolation of the isomeric disulfide 14. The reactive entity was regarded as the sulfenic acid rather than sulfenate anion under these reaction conditions.

• 한국재료학회지
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• 제26권2호
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• pp.73-78
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• 2016

$TiO_2$ nanoparticles were synthesized by a sol-gel process using titanium tetra isopropoxide as a precursor at room temperature. Ag-doped $TiO_2$ nanoparticles were prepared by photoreduction of $AgNO_3$ on $TiO_2$ under UV light irradiation and calcinated at $400^{\circ}C$. Ag-doped $TiO_2$ nanoparticles were characterized for their structural and morphological properties by X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM). The photocatalytic properties of the $TiO_2$ and Ag-doped $TiO_2$ nanoparticles were evaluated according to the degree of photocatalytic degradation of gaseous benzene under UV and visible light irradiation. To estimate the rate of photolysis under UV (${\lambda}=365nm$) and visible (${\lambda}{\geq}410nm$) light, the residual concentration of benzene was monitored by gas chromatography (GC). Both undoped/doped nanoparticles showed about 80 % of photolysis of benzene under UV light. However, under visible light irradiation Ag-doped $TiO_2$ nanoparticles exhibited a photocatalytic reaction toward the photodegradation of benzene more efficient than that of bare $TiO_2$. The enhanced photocatalytic reaction of Ag-doped $TiO_2$ nanoparticles is attributed to the decrease in the activation energy and to the existence of Ag in the $TiO_2$ host lattice, which increases the absorption capacity in the visible region by acting as an electron trapper and promotes charge separation of the photoinduced electrons ($e^-$) and holes ($h^+$). The use of Ag-doped $TiO_2$ nanoparticles preserved the option of an environmentally benign photocatalytic reaction using visible light; These particles can be applicable to environmental cleaning applications.

• 한국재료학회지
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• 제22권7호
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• pp.352-357
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• 2012

$SnO_2$-mixed and Sn-doped $TiO_2$ nanoparticles were synthesized via a hydrothermal process. $SnO_2$-mixed $TiO_2$ nanoparticles prepared in a neutral condition consisted of anatase $TiO_2$ nanoparticles(diamond shape, ~25 nm) and cassiterite $SnO_2$ nanoparticles(spherical shape, ~10 nm). On the other hand, Sn-doped $TiO_2$ nanoparticles obtained under a high acidic condition showed a crystalline phase corresponding to rutile $TiO_2$. As the Sn content increased, the particle shape changed from rod-like(d~40 nm, 1~200 nm) to spherical(18 nm) with a decrease in the particle size. The peak shift in the XRD results and a change of the c-axis lattice parameter with the Sn content demonstrate that the $TiO_2$ in the rutile phase was doped with Sn. The photocatalytic activity of the $SnO_2$-mixed $TiO_2$ nanoparticles dramatically increased and then decreased when the $SnO_2$ content exceeded 4%. The increased photocatalytic activity is mainly attributed to the improved charge separation of the $TiO_2$ nanoparticles with the $SnO_2$. In the case of Sn-doped $TiO_2$ nanoparticles, the photocatalytic activity increased slightly with the Sn content due most likely to the larger energy bandgap caused by Sn-doping and the decrease in the particle size. The $SnO_2$-mixed $TiO_2$ nanoparticles generally exhibited higher photocatalytic activity than the Sn-doped $TiO_2$ nanoparticles. This was caused by the phase difference of $TiO_2$.

• Korean Journal of Chemical Engineering
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• 제35권12호
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• pp.2442-2451
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• 2018

Novel highly active visible-light photocatalysts in the form of zinc bismuth oxide ($ZnBi_2O_4$) and graphite hybrid composites were prepared by coupling via a co-precipitation method followed by calcination at $450^{\circ}C$. The asprepared $ZnBi_2O_4$-graphite hybrid composites were tested for the degradation of rhodamine B (RhB) solutions under visible-light irradiation. The existence of strong electronic coupling between the two components within the $ZnBi_2O_4$-graphite heterostructure suppressed the photogenerated recombination of electrons and holes to a remarkable extent. The prepared composite exhibited excellent photocatalytic activity, leading to more than 93% of RhB degradation at an initial concentration of $50mg{\cdot}L^{-1}$ with 1.0 g catalyst per liter in 150 min. The excellent visible-light photocatalytic mineralization of $ZnBi_2O_4-1.0graphite$ in comparison with pristine $ZnBi_2O_4$ could be attributed to synergetic effects, charge transfer between $ZnBi_2O_4$ and graphite, and the separation efficiency of the photogenerated electrons and holes. The photo-induced $h^+$ and the superoxide anion were the major active species responsible for the photodegradation process. The results demonstrate the feasibility of $ZnBi_2O_4-1.0graphite$ as a potential heterogeneous photocatalyst for environmental remediation.

• Geomechanics and Engineering
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• 제2권1호
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• pp.1-18
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• 2010

The analysis of structure response and design of buried structures subjected to dynamic destructive loads have been receiving increasing interest due to recent severe damage caused by strong earthquakes and terrorist attacks. For a comprehensive design of buried structures subjected to blast loads to be conducted, the whole system behaviour including simulation of the explosion, propagation of shock waves through the soil medium, the interaction of the soil with the buried structure and the structure response needs to be simulated in a single model. Such a model will enable more realistic simulation of the fundamental physical behaviour. This paper presents a complete model simulating the whole system using the finite element package ABAQUS/Explicit. The Arbitrary Lagrange Euler Coupling formulation is used to model the explosive charge and the soil region near the explosion to eliminate the distortion of the mesh under high deformation, while the conventional finite element method is used to model the rest of the system. The elasto-plastic Drucker-Prager Cap model is used to model the soil behaviour. The explosion process is simulated using the Jones-Wilkens-Lee equation of state. The Concrete Damage Plasticity model is used to simulate the behaviour of concrete with the reinforcement considered as an elasto-plastic material. The contact interface between soil and structure is simulated using the general Mohr-Coulomb friction concept, which allows for sliding, separation and rebound between the buried structure surface and the surrounding soil. The behaviour of the whole system is evaluated using a numerical example which shows that the proposed model is capable of producing a realistic simulation of the physical system behaviour in a smooth numerical process.

• 한국재료학회지
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• 제29권3호
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• pp.196-203
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• 2019

We report on the fabrication and characterization of an oxide photoanode with a zinc oxide (ZnO) nanorod array embedded in cuprous oxide ($Cu_2O$) thin film, namely a $ZnO/Cu_2O$ oxide p-n heterostructure photoanode, for enhanced efficiency of visible light driven photoelectrochemical (PEC) water splitting. A vertically oriented n-type ZnO nanorod array is first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film is directly electrodeposited onto the vertically oriented ZnO nanorod array to form an oxide p-n heterostructure. The introduction of $Cu_2O$ layer produces a noticeable enhancement in the visible light absorption. From the observed PEC current density versus voltage (J-V) behavior under visible light illumination, the photoconversion efficiency of this $ZnO/Cu_2O$ p-n heterostructure photoanode is found to reach 0.39 %, which is seven times that of a pristine ZnO nanorod photoanode. In particular, a significant PEC performance is observed even at an applied bias of 0 V vs $Hg/Hg_2Cl_2$, which makes the device self-powered. The observed improvement in the PEC performance is attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential including the light absorption and separation processes of photoinduced charge carriers, which provides a new avenue for preparing efficient photoanodes for PEC water splitting.

• 한국환경과학회지
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• 제27권11호
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• pp.967-974
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• 2018

In this study, we evaluated the photocatalytic oxidation efficiency of aromatic volatile hydrocarbons by using $WO_3$-doped $TiO_2$ nanotubes (WTNTs) under visible-light irradiation. One-dimensional WTNTs were synthesized by ultrasonic-assisted hydrothermal method and impregnation. XRD analysis revealed successful incorporation of $WO_3$ into $TiO_2$ nanotube (TNT) structures. UV-Vis spectra exhibited that the synthesized WTNT samples can be activated under visible light irradiation. FE-SEM and TEM images showed the one-dimensional structure of the prepared TNTs and WTNTs. The photocatalytic oxidation efficiencies of toluene, ethylbenzene, and o-xylene were higher using WTNT samples than undoped TNT. These results were explained based on the charge separation ability, adsorption capability, and light absorption of the sample photocatalysts. Among the different light sources, light-emitting-diodes (LEDs) are more highly energy-efficient than 8-W daylight used for the photocatalytic oxidation of toluene, ethylbenzene, and o-xylene, though the photocatalytic oxidation efficiency is higher for 8-W daylight.

• Geomechanics and Engineering
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• 제19권1호
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• pp.49-60
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• 2019

Crack instability propagation during coal and rock mass failure is the main reason for electromagnetic radiation (EMR) generation. However, original cracks on coal and rock mass are hard to study, making it complex to reveal EMR laws and mechanisms. In this paper, we prefabricated cracks of different inclinations in coal and rock samples as the analogues of the native cracks, carried out uniaxial compression experiments using these coal and rock samples, explored, the effects of the prefabricated cracks on EMR laws, and verified these laws by measuring the surface potential signals. The results show that prefabricated cracks are the main factor leading to the failure of coal and rock samples. When the inclination between the prefabricated crack and axial stress is smaller, the wing cracks occur first from the two tips of the prefabricated crack and expand to shear cracks or coplanar secondary cracks whose advance directions are coplanar or nearly coplanar with the prefabricated crack's direction. The sample failure is mainly due to the composited tensile and shear destructions of the wing cracks. When the inclination becomes bigger, the wing cracks appear at the early stage, extend to the direction of the maximum principal stress, and eventually run through both ends of the sample, resulting in the sample's tensile failure. The effect of prefabricated cracks of different inclinations on electromagnetic (EM) signals is different. For samples with prefabricated cracks of smaller inclination, EMR is mainly generated due to the variable motion of free charges generated due to crushing, friction, and slippage between the crack walls. For samples with larger inclination, EMR is generated due to friction and slippage in between the crack walls as well as the charge separation caused by tensile extension at the cracks' tips before sample failure. These conclusions are further verified by the surface potential distribution during the loading process.

• 멤브레인
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• 제28권6호
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• pp.414-423
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• 2018

본 연구에서는 염색 염료 산업의 폐수 처리 및 재활용 공정에 분리막을 적용하고자 실란 커플링제를 이용하여 상용화된 나노복합막을 표면 개질하였다. 실란 커플링제는 말단 관능기가 다른 octyltrimethoxysilane (OcTMS)와 (3-aminopropyl) trimethoxysilane (APTMS)을 사용하였으며, 표면 개질을 통해 염료 분리 및 내오염성을 향상시키고자 하였다. XPS, FE-SEM, EDX 분석을 통하여 막 표면의 화학 구조 변화 및 실란 적층을 확인하였고, AFM 분석을 통해 개질막의 표면 모폴로지를 확인하였다. Zeta potential을 통해 실란 개질 막이 상용막 대비 표면 전하가 중성으로 변하는 것을 확인하였다. 그 결과, OcTMS와 APTMS로 개질한 막의 내오염성은 NE70에 비해 약 2배 이상 향상되었다. 또한, 실란으로 표면 개질한 나노복합막은 음이온 염료(Orange II) 용액에서 약 90% 이상, 양이온 염료(Safranin-O) 용액에서 약 98% 이상의 염료 제거율을 나타내어 양이온 염료 용액 처리에 적합한 것을 확인하였다.

• Korean Journal of Chemical Engineering
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• 제35권11호
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• pp.2283-2289
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• 2018

$TiO_2$ microspheres were successfully synthesised by simple solution phase method by using various amount of titanium butoxide as precursor. The prepared $TiO_2$ were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance absorption spectra (UV-DRS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XRD analysis revealed that the as-synthesized $TiO_2$ microsphere poses an anatase phase. The photocatalytic degradation experiments were carried out with three different dyes, such as methylene blue, brilliant black, reactive red-120 for four hours under UV light irradiation. The results show that $TiO_2$ morphology had great influence on photocatalytic degradation of organic dyes. The experimental results of dye mineralization indicated the concentration was reduced by a high portion of up to 99% within 4 hours. On the basis of various characterization of the photocatalysts, the reactions involved to explain the photocatalytic activity enhancement due to the concentration of titanium butoxide and morphology include a better separation of photogenerated charge carriers and improved oxygen reduction inducing a higher extent of degradation of aromatics.