• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.152-152
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• 2013

Mechanism of energy conversion from chemical to electrical during exothermic catalytic reactions at the metal surfaces has been a fascinating and crucial subject in heterogeneous catalysis. A metal-semiconductor Schottky nanodiode is novel device for direct detection of chemically induced hot electrons which have sufficient energy to surmount the Schottky barrier. We measured a continuous chemicurrent during the hydrogen oxidation under of 760 Torr of O2 and 6 Torr of H2 by using Pt/Si and Pt/TiO2 nanodiodes at reaction temperatures and compared the chemicurrent with the reaction turnover rate. The thermoelectric current was measured by carrying out an experiment under O2 condition for elimination of the background current. Gas chromatograph and source meter were used for measurement of the chemical turnover rate and the chemicurrent, respectively. The correlation between the chemicurrent and the chemical turnover rate under hydrogen oxidation implies how hot electrons generated on the metal surface affect hydrogen oxidation.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.140.2-140.2
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• 2013

Strong metal-support interaction effect is an important issue in determining the catalytic activity for heterogeneous catalysis. In this work, we report the catalytic activity of $Au/TiO_2$, $Au/Al_2O_3$, and $Au/Al_2O_3-CeO_2$ nanocatalysts under CO oxidation fabricated by arc plasma deposition (APD), which is a facile dry process with no organic materials involved. These catalytic materials were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and $N_2$-physisorption. Catalytic activity of the materials has measured by CO oxidation using oxygen, as a model reaction, in a micro-flow reactor at atmospheric pressure. Using APD, the catalyst nanoparticles were well dispersed on metal oxide powder with an average particle size (3~10 nm). As for catalytic reactivity, the result shows $Au/Al_2O_3-CeO_2$ nanocatalyst has the highest catalytic activity among three samples in CO oxidation, and $Au/TiO_2$, and $Au/Al_2O_3$ in sequence. We discuss the effects of structure and metal-oxide interactions of the catalysts on catalytic activity.

• Biomolecules & Therapeutics
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• 제27권5호
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• pp.492-501
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• 2019

Nitrogen-containing heterocycles such as quinoline, quinazolinones and indole are scaffolds of natural products and have broad biological effects. During the last years those structures have been intensively synthesized and modified to yield new synthetic molecules that can specifically inhibit the activity of dysregulated protein kinases in cancer cells. Herein, a series of newly synthesized isoquinolinamine (FX-1 to 8) and isoindoloquinazolinone (FX-9, FX-42, FX-43) compounds were evaluated in regards to their anti-leukemic potential on human B- and T- acute lymphoblastic leukemia (ALL) cells. Several biological effects were observed. B-ALL cells (SEM, RS4;11) were more sensitive against isoquinolinamine compounds than T-ALL cells (Jurkat, CEM). In SEM cells, metabolic activity decreased with $10{\mu}M$ up to 26.7% (FX-3), 25.2% (FX-7) and 14.5% (FX-8). The 3-(p-Tolyl) isoquinolin-1-amine FX-9 was the most effective agent against B- and T-ALL cells with IC50 values ranging from 0.54 to $1.94{\mu}M$. None of the tested compounds displayed hemolysis on erythrocytes or cytotoxicity against healthy leukocytes. Anti-proliferative effect of FX-9 was associated with changes in cell morphology and apoptosis induction. Further, influence of FX-9 on PI3K/AKT, MAPK and JAK/STAT signaling was detected but was heterogeneous. Functional inhibition testing of 58 kinases revealed no specific inhibitory activity among cancer-related kinases. In conclusion, FX-9 displays significant antileukemic activity in B- and T-ALL cells and should be further evaluated in regards to the mechanisms of action. Further compounds of the current series might serve as templates for the design of new compounds and as basic structures for modification approaches.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.264-264
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• 2013

Strong metal-support interaction effect is an important issue in determining the catalytic ac-tivity for heterogeneous catalysis. In this study, we investigated the support effect and the role of organic capping layers of two-dimensional Pt nanocatalysts on reducible metal oxide supports under the CO oxidation. Several reducible metal oxide supports including CeO2, Nb2O5, and TiO2 thin films were prepared via sol-gel techniques. The structure, chemical state and optical property were characterized using XRD, XPS, TEM, SEM, and UV-VIS spectrometer. We found that the reducible metal oxide supports have a homogeneous thin thickness and crystalline structure after annealing at high temperature showing the different optical band gap energy. Langmuir-Blodgett technique and arc plasma deposition process were employed to ob-tain Pt nanoparticle arrays with capping and without capping layers, respectively on the oxide support to assess the role of the supports and capping layers on the catalytic activity of Pt catalysts under the CO oxidation. The catalytic performance of CO oxidation over Pt supported on metal oxide thin films under oxidizing reaction conditions (40 Torr CO and 100 Torr O2) was tested. The results show that the catalytic activity significantly depends on the metal oxide support and organic capping layers of Pt nanoparticles, revealing the strong metal-support interaction on these nanocatalysts systems.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.164-164
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• 2013

Among multicomponent nanostructures, hybrid nanocatalysts consisting of metal nanoparticle-semiconductor junctions offer an interesting platform to study the role of metal-oxide interfaces and hot electron flows in heterogeneous catalysis. In this study, we report that hot carriers generated upon photon absorption significantly impact the catalytic activity of CO oxidation. We found that Pt-CdSe-Pt nanodumbbells exhibited a higher turnover frequency by a factor of two during irradiation by light with energy higher than the bandgap of CdSe, while the turnover rate on bare Pt nanoparticles didn't depend on light irradiation. We also found that Pt nanoparticles deposited on a GaN substrate under light irradiation exhibit changes in catalytic activity of CO oxidation that depends on the type of doping of the GaN. We suppose that hot electrons are generated upon the absorption of photons by the semiconducting nanorods or substrates, whereafter the hot electrons are injected into the Pt nanoparticles, resulting in the change in catalytic activity. We discuss the possible mechanism for how hot carrier flows generated during light irradiation affect the catalytic activity of CO oxidation.

• Korean Chemical Engineering Research
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• 제45권4호
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• pp.410-413
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• 2007

불균일계 중합촉매내 내부전자공여체(ID)의 존재 유무와 종류가 에틸렌과 1-부텐 간의 공중합에서 얻어지는 공중합물에 미치는 영향에 대하여 살펴보았다. 실리카 담지 $TiCl_4$ 촉매를 실리카 담지체에 ethylaluminium dichloride, magnesium alkyl, 2-ethyl-1-hexanol, $TiCl_4$와 여러 종류의 ID 등을 이용하여 제조하였으며 이 때 ID와 Ti의 몰비를 0.5로 고정하였다. ID는 ethylbenzoate(EB), diisobuylphthalate(DIBP), dioctylphthalate(DOP)을 사용하였다. ID가 촉매 내에 존재하는 경우 Ti(+3)의 함량비가 증가하였다. 공중합 활성은 EB를 $TiCl_4$ 반응 후에 투입한 촉매가 가장 높았으며 그 외의 ID가 존재하는 촉매는 활성이 감소하는 현상을 보였다. Xylene soluble(XS) 측정값은 ID가 존재하는 모든 중합촉매가 ID가 없는 경우 보다 50% 이상 감소하였으며 Crystaf 분석 결과 DIBP가 존재하는 촉매가 상대적으로 균일한 화학조성분포를 보였다. 이는 ID가 분균일한 촉매활성점을 보다 균일하게 만드는 역할에서 기인한 것으로 보이며 입체규칙성을 갖는 활성점을 만들거나 비입체규칙성 활성점을 blocking하는 역할 때문인 것으로 설명할 수 있다.

• Carbon letters
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• 제4권1호
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• pp.1-9
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• 2003

Recently, the control of pore-characteristics of nano-porous materials has been studied extensively because of their unique applications, which includes size-selective separation, gas adsorption/storage, heterogeneous catalysis, etc. The most widely adopted techniques for controlling pore characteristics include the utilization of pillar effect by metal oxide and of templates such as zeolites. More recently, coordination polymers constructed by transition metal ions and bridging organic ligands have afforded new types of nano-porous materials, porous metal-organic framework(porous MOF), with high degree and uniformity of porosity. The pore characteristics of these porous MOFs can be designed by controlling the coordination number and geometry of selected metal, e.g transition metal and rare-earth metal, and the size, rigidity, and coordination site of ligand. The synthesis of porous MOF by the assembly of metal ions with di-, tri-, and poly-topic N-bound organic linkers such as 4,4'-bipyridine(BPY) or multidentate linkers such as carboxylates, which allow for the formation of more rigid frameworks due to their ability to aggregate metal ions into M-O-C cluster, have been reported. Other porous MOF from co-ligand system or the ligand with both C-O and C-N type linkage can afford to control the shape and size of pores. Furthermore, for the rigidity and thermal stability of porous MOF, ring-type ligand such as porphyrin derivatives and ligands with ability of secondary bonding such as hydrogen and ionic bonding have been studied.

• 한국재료학회지
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• 제32권2호
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• pp.98-106
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• 2022

Metal-organic frameworks (MOFs) are widely used in various fields because they make it easy to control porous structures according to combinations of metal ions and organic linkers. In addition, ZIF (zeolitic imidazolate framework), a type of MOF, is made up of transition metal ions such as Co²⁺ or Zn²⁺ and linkers such as imidazole or imidazole derivatives. ZIF-67, composed of Co²⁺ and 2-methyl imidazole, exhibits both chemical stability and catalytic activity. Recently, due to increasing need for energy technology and carbon-neutral policies, catalysis applications have attracted tremendous research attention. Moreover, demand is increasing for material development in the electrocatalytic water splitting and metal-air battery fields; there is also a need for bifunctional catalysts capable of both oxidation/reduction reactions. This review summarizes recent progress of bifunctional catalysts for electrocatalytic water splitting and metal-air batteries using ZIF-67. In particular, the field is classified into areas of thermal decomposition, introduction of heterogeneous elements, and complex formation with carbon-based materials or polyacrylonitrile. This review also focuses on synthetic methods and performance evaluation.

• 한국환경과학회지
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• 제14권2호
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• pp.221-230
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• 2005

Catalytic wet oxidation of trichloroethylene (TCE) in water has been conducted using $TiO_2-supported$ cobalt oxides at $36^{\circ}C$ with a weight hourly space velocity of $7,500\;h^{-1}.\;5\%\;CoO_x/TiO_2$, prepared by using an incipient wetness technique, might be the most promising catalyst for the wet oxidation although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. XPS spectra of both fresh and used Co surfaces gave different surface spectral features for each $CoO_x,\;Co\;2P_{3/2}$ binding energy for Co species in the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $CO_2TiO_4\;and\;CoTiO_3$. The used catalyst exhibited a 780.3-eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD patterns for $5\%\;CoO_x/TiO_2$ catalyst indicated that the phase structure of Co species in the catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present predominantly on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

• 대한환경공학회지
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• 제27권3호
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• pp.253-261
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• 2005

불균일 $CoO_x/TiO_2$ 촉매가 충진된 연속 흐름식 고정층 반응기 내에서 ppm 수준으로 수중에 존재하는 trichloroethylene (TCE) 제거반응을 수행하였으며, 가장 우수한 반응활성을 갖는 촉매의 결정구조와 표면화학적 특성을 분석함으로써 반응시간에 따라 분해활성이 전이영역을 보이는 원인을 규명하고자 하였다. $36^{\circ}C$의 반응온도에서 모델반응의 내부확산저항은 없었으며, $TiO_2$ 표면에 흡착에 의한 액상 TCE 제거정도는 무시할 수 있었다. 5% $CoO_x/TiO_2$ 촉매는 본 대상반응에 대하여 가장 우수한 활성을 갖는 것으로 나타났으며, 반응시간의 경과정도에 따라 TCE 분해효율이 점진적으로 증가하여 안정화되는 전이영역의 존재를 확인할 수 있었다. 반응 전 5% $CoO_x$ 촉매에 대한 XRD 패턴에서 담지체로 사용된 $TiO_2$에 의한 피크들 외에 새로운 피크가 관찰되었고, 5시간 이상 동안 반응한 후에 건조된 촉매의 경우에도 반응 전 촉매의 XRD 피크와 매우 유사하였다. $Co_3O_4$의 XRD 패턴들과 대조한 결과, 5% $CoO_x$ 촉매상에서 Co 화합물에 의해 야기되는 XRD 피크들은 $Co_3O_4$에 의한 것임을 알 수 있었다. 반응물에 노출되지 않은 5% $CoO_x/TiO_2$ 촉매에 대한 XPS 측정은 797.1 eV에서 Co $2p_{1/2}$에 대한 주피크와 함께 781.3 eV에서 Co $2p_{3/2}$에 대한 주피크가 관찰되어졌다. 반응 후 촉매의 경우에는 Co $2p_{3/2}$ 및 Co $2p_{1/2}$의 binding energy들은 각각 780.3과 795.8 eV에서 나타났다. 반응 전 후 촉매상에서 Co $2p_{3/2}$의 binding energy 차이는 1.0 eV이고, Co $2p_{1/2}$의 binding energy 차이는 1.3 eV이다. 표준 $Co_3O_4$에 대한 XPS 측정결과, 반응 후 촉매상에 존재하는 $CoO_x$는 $Co_3O_4$로 존재하고, 반응 전의 경우에는 이와는 다른 chemical state를 보여주었다. XRD 및 XPS 결과를 바탕으로, 촉매표면에 존재하는 $Co_3O_4$의 외부표면이 $Co_2TiO_4$와 $CoTiO_3$ 같은 $CoTiO_x$로 encapsulation되어 있는 모델구조를 제안할 수 있고, 이는 반응시간의 함수로 나타나는 촉매활성에 있어서 전이영역의 존재를 잘 설명할 수 있을 뿐만 아니라, XRD와 XPS에서 얻어진 촉매의 물리화학적인 특성을 잘 반영할 수 있다.