• 한국진공학회:학술대회논문집
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• 한국진공학회 2010년도 제39회 하계학술대회 초록집
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• pp.87-87
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• 2010

Adsorption and subsequent catalytic reactions of ethanol and acetaldehyde on chemically modified rutile TiO2(001) surfaces are probed by x-ray photoemission spectroscopy (XPS) using synchrotron radiation. TiO2 is a well-known photocatalyst for various catalytic reactions including oxidation of organic molecules. In this respect, the surface atomic structure has been found to play a vital role in determining the catalytic reactivity and selectivity of TiO2. In this study, we employ an atomically well-ordered reduced TiO2(001) surface which is prepared in a UHV chamber by repeated Ar+-sputtering and annealing (900 K) cycles. We systematically modify the surface by treating the surface with H2O or O2 at room temperature (RT). The catalytic reactivity of the surface-modified TiO2(001) is evaluated by dosing ethanol/acetaldehyde onto the surface at RT and by subsequent annealing to higher temperatures (400~600 K). XPS spectra of C 1s core level are intensively used to probe any change in the oxidation state of carbon atoms. We find that the reactivity as well as the saturation coverage are significantly affected by the RT-treatment of the TiO2 surface with H2O or O2. For both reactant molecules (ethanol/acetaldehyde), oxidation reactions are found to be enhanced on the O2-treated surface compared with the reduced or H2O-treated surfaces. Possibly reaction pathways are discussed based on the observed XPS spectra.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2443-2447
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2410-2414
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

• Korean Chemical Engineering Research
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• 제44권4호
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• pp.356-362
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• 2006

본 연구에서는 석탄가스화복합발전(integrated gas combined cycle, 이하 IGCC) 시스템의 석탄가스화기로부터 생산되는 석탄가스가 환원제로 이용되는 $SO_2$ 환원공정인 직접 황 회수 공정(direct sulfur recovery process, 이하 DSRP)에서 이용 가능한 Sn-Zr계 촉매 상에서의 $SO_2$ 환원반응특성을 조사하였다. Sn-Zr계 촉매는 0/1, 1/4, 1/1, 2/1, 3/1, 1/0의 Sn/Zr 몰비로 조절하여 침전법 및 공침법으로 제조되었다. 공간속도가 $10,000ml/g_{-cat.}{\cdot}h$, 반응물 몰비$([CO(or\;H_2)]/[SO_2])$가 2.0인 반응조건 하에서 Sn-Zr계 촉매를 이용하여 온도를 변화시킨 가운데 석탄가스에 포함되어 있는 $H_2$ 또는 CO를 환원제로 사용하여 $SO_2$ 환원에 대한 반응특성이 조사되었다. 실험 결과, 환원제의 종류에 상관없이 $SnO_2$와 $ZrO_2$보다 Sn-Zr계 촉매가 활성이 더 높았으며, 환원제의 종류에 대한 반응성 조사 결과, $H_2$보다 CO가 $SO_2$ 환원에 더 높은 반응성을 나타내었다. $H_2$가 환원제로 이용된 $SO_2$ 환원특성을 조사한 결과, Sn/Zr 비에 따라 제조된 Sn-Zr계 촉매의 종류에 상관없이 온도가 증가함에 따라 반응성이 증가하는 경향을 보이며 Sn/Zr 몰비가 1/4인 촉매를 사용한 경우 $550^{\circ}C$에서 $SO_2$전환율이 94.4％, 원소 황 수율이 66.4％로 높은 반응성을 나타내었다. 반면 CO를 환원제로 이용한 경우에는 Sn/Zr 몰비가 높은 촉매일수록 최적 반응온도가 감소되는 특이한 경향을 나타내었다. Sn-Zr계 촉매 중 Sn/Zr 몰비가 3/1인 $SnO_2-ZrO_2$ 촉매가 가장 낮은 최적 반응온도에서 높은 반응성을 나타내었는데, $325^{\circ}C$에서 $SO_2$전환율이 약 100％, 원소 황 수율이 약 99.5％로 가장 높은 반응성을 얻었다. 그리고 CO가 $H_2$보다 더 많이 포함되어 있는 석탄모사가스에 대하여 환원제로서의 이용가능성을 확인하고자 $CO/H_2$ 비를 달리한 각각의 합성가스에 대하여 $SO_2$ 환원반응실험을 수행하였다. Sn/Zr 몰비가 2/1인 Sn-Zr계 촉매 상에서 $SO_2$ 환원반응 실험 결과, CO 함량이 높은 합성가스일수록 효과적인 환원제임을 확인할 수 있었다. 따라서 Sn-Zr계 촉매가 적용된 DSRP에서 석탄모사가스가 환원제로 이용 가능하다는 것을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제17권3호
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• pp.234-238
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reaction of p-nitrophenyl acetate (PNPA) with morpholine, piperazine and piperidine in MeCN-H2O mixtures of varying compositions. The rate of the present aminolysis decreases upon additions of MeCN into H2O up to near 30-40 mole % MeCN and remains nearly constant upon further additions of MeCN. The reaction of PNPA with anionic nucleophiles, such as HO-, p-chlorophenoxide and butane-2,3-dione monoximate, has also exhibited two distinguishable reactivity zones. However, the reactivity trend for the anionic nucleophiles is quite different from the one obtained for the amine system, e.g. an initial rate decrease in the H2O-rich region followed by an increasing rate trend upon further additions of MeCN in the MeCN-rich region. The rate behaviors shown by the amine system in the MeCN-rich and by the anionic system in the H2O-rich region are unexpected based on the Hughes-Ingold rules. The present unusual rate trends have been attributed to changes in the solvent structure and pKa of the nucleophiles upon the addition of MeCN into H2O. The effect of solvent appears to be more significant for the TS than the GS, and the TS structure is considered to become tighter in the higher MeCN concentration.

• 대한약리학회지
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• 제19권2호
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• pp.35-44
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• 1983

reactive oxygen species에 의해 나타나는 reactivity에 있어서 metal ions이 관여함이 시사되고 있다. 이미 알려진 reactive oxygen species와 metal ions의 상호작용 이외에 특히 $Cu^{++}$과 $H_2O_2$가 강력한 peroxidative action을 나타낸다는 사실이 알려져 있으며 $Cu^{++}-H_2O_2$가 biological system 에서의 조직파괴에 관여할 가능성이 저자들에 의해서 효소 및 조직치 구조 단백질의 gradation 효과를 관찰함으로써 시사되었다. 본 연구는 $H_2O_2$ 혹은 $H_2O_2$를 생성하는 효소계(xanthine과 xanthine oxidase 및 glucose과 glucose oxidase)에 $Cu^{++}$을 첨가하여 $Cu^{++}-H_2O_2$에 의한 peroxidation의 효과를 collagen gelation을 통하여 확인코저 수행하였으며 다음과 같은 결과를 얻었다. 1) $Cu^{++}(20\;{\mu}M)$과 $H_2O_2$에 의하며 collagen gelation은 현저히 억제되었으며 이같은 억제효과는 양자의 농도에 비례하였다. 2) $Cu^{++}-H_2O_2$ reactivity를 확인하는 다른 방법으로 glucose oxidase system를 이용하였다. glucose oxidase$(2.5{\mu}g/ml)$ 와 glucose(0.5 mM)는 collagen gelation에 영향을 미치지 않았으나 이에 $Cu^{++}$이 존재하면 gelation이 억제되었다. 이때 억제정도는 $glucose(0.125{\sim}l.25\;mM)$와 $Cu^{++}$의 농도에 비례하였다. 3) 여러 reactive oxygen species 가운데 $Cu^{++}-H_2O_2$ reactivity를 xanthine oxidase system을 이용하여 확인하였다. (a) collagen gelation은 xanthine oxidase(30 munits/ml)와 xanthine$(0.25{\sim}2\;mM)$에 의하여 억제되었다. (b) 이때 나타나는 collagen gelation의 억제는 superoxide dismutase에 의하여 완전히 회복되었으나 catalase에 의해서는 더욱 촉진되었다. 그러나 catalase에 의한 억제효과의 촉진은 1,4-diazabicyclo(2,2,2)octane에 의하여 완전히 소실되었다. 따라서 이 xanthine oxidase system에서는 $O_2-,\;H_2O_2,\;^1O_2$이 관여함을 알 수 있었다. (c) 그러나 $Cu^{++}(10\;{\mu}M)$이 존재하였을 때 collagen gelation은 superoxie dismutase에 의해 더욱 억제되었고 catalase에 의해서는 완전히 회복되었다. xanthine oxidase계에서 얻어진 결과는 여러 reactive oxygen species가운데 $H_2O_2$가 $Cu^{++}$에 의하여 peroxidation효과를 나타냄을 알 수 있었다. 이상의 결과로 미루어 볼 때 reactive oxygen species와 metal ions과의 상호작용 가운데 $Cu^{++}-H_2O_2$는 강한 반응을 나타내는 특이한 구성요소이고 헌재 시사되고 있는 reactive oxygen species의 biological effects에 비추어 $Cu^{++}-catalyzed peroxidation$도 병적상태에서 생체에 유해한 작용을 나타내는 요소임을 시사하며 특히 염증시 조직파괴역할에 관하여 고찰하였다.

• 한국수소및신에너지학회논문집
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• 제22권1호
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• pp.92-99
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• 2011

Barium cerate ($BaCeO_3$) related perovskite ceramics currently dominate the high-temperature proton conductor field. Unfortunately, these materials have very stringent environmental limitations necessitating the costly and complex conditioning or cleaning of the application feed-gas. Commercial realization has been hampered, in part, because of the reactivity of $BaCeO_3$ with $CO_2$, and to some extent $H_2O$. And sintered $BaCeO_3$ decomposed at a rate comparable to the powder samples. In this article, the chemical stability and the structural changes of $BaCe_{0.9-X}Y0.1La_XO_{3-\delta}$ (X=0, 0.1, 0.2) have been systematically investigated in the atmosphere containing carbon dioxide ($CO_2$) and water vapor ($H_2O$). The sintering characteristics were studied in $1600^{\circ}C$, sintered pellets disintegrate and decompose upon contacting boiling water on the surface only.

• Bulletin of the Korean Chemical Society
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• 제24권2호
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• pp.197-204
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• 2003

The intracluster ion-molecule reactions of $Ti^+(H_2O)_n,\;Ti^+(CH_3OCH_3)_n,\;and\;Ti^+(CH_3OD)_n$ complexes produced by the mixing of the laser-vaporized plasma and the pulsed supersonic beam were studied using a reflectron time-of-flight mass spectrometer. The reactions of $Ti^+$ with water clusters were dominated by the dehydrogenation reaction, which produces $TiO^+(H_2O)_n$ clusters. The mass spectra resulting from the reactions of $Ti^+\;with\;CH_3OCH_3$ clusters exhibit a major sequence of $Ti^+(OCH_3)_m(CH_3OCH_3)_n$ cluster ions, which is attributed to the insertion of $Ti^+$ ion into C-O bond of $CH_3OCH_3$ followed by $CH_3$ elimination. The prevalence of $Ti^+(OCH_3)_m(CH_3OD)_n$ ions in the reaction of $Ti^+\;with\;CH_3OD$ clusters suggests that D elimination via O-D bond insertion is the preferred decomposition pathway. In addition, the results indicate that consecutive insertion reactions by the $Ti^+$ ion occur for up to three precursor molecules. Thus, examination of $Ti^+$ insertion into three different molecules establishes the reactivity order: O-H > C-O > C-H. The experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.

• 한국세라믹학회지
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• 제39권5호
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• pp.452-459
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• 2002

고로슬래그와 플라이 애쉬의 석회 반응성을 수열조건 하에서 각각 고찰하였다. 수열반응 조건은 CaO-$SiO_2$ 비(C/S), 수열온도($140{\circ}C$와 $180{\circ}C$)및 반응시간(20~60시간)이었다. 수열반응성은 각 수경성 재료에 함유된 $SiO_2$와 (순수)석회 사이의 반응률 및 반응 시편의 압축강도를 측정하여 조사하였다. 그리고 본 반응성 고찰을 위하여 기공률 측정 및 XRD 분석도 수행하였다. 압축강도 물성은 시편의 기공률 및 CaO-$SiO_2$ 반응성과 연계하여 고찰하였으며, XRD 분석으로 수열반응 중 C/S가 변화함을 확인할 수 있었다. 고로슬래그 중의 $SiO_2$는 플라이 애쉬에 함유된 $SiO_2$ 보다 석회반응성이 우수하여 전자의 경우 시편은 훨씬 높은 강도를 나타내었다. 수열반응 온도 $180{\circ}C$ 및 40시간의 조건에서 고로슬래그는 최고 강도 $807kg/cm^2$을 나타냈으며, 플라이 애쉬의 경우 최고 강도는 $397kg/cm^2$ 이었다.

• Environmental Engineering Research
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• 제18권1호
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• pp.29-35
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• 2013

This study noted that the actual mechanism of N-nitrosodimethylamine (NDMA) photodecomposition in the presence of $H_2O_2$ is missing from the previous works. This study investigated a key unknown reactive species (URS) enhanced by the addition of $H_2O_2$ during the photolysis of NDMA with $H_2O_2$, not hydroxyl radicals. In order to provide experimental evidences in support of URS formation, we have mainly used p-nitrosodimethylaniline, methanol, and benzoic acid as well-known probes of ${\cdot}OH$ in this study. Both loss of PNDA and formation of hydroxybenzoic acids were dependent on NDMA concentrations during the photolysis in a constant concentration of $H_2O_2$. In particular, competition kinetics showed that the relative reactivity of an URS was at least identical with ${\cdot}OH$-like reactivity. In addition, the decay of NDMA was estimated to be about 65% by the direct UV light and about 35% by the reactive species or URS generated through the photolysis of NDMA and $H_2O_2$. Therefore, our data suggest that a highly oxidizing URS is formed in the photolysis of NDMA with $H_2O_2$, which could be peroxynitrite ($ONOO^-$) as a potent oxidant by itself as well as a source of ${\cdot}OH$.