• 청정기술
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• 제22권4호
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• pp.250-257
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• 2016

As an attempt to replacing petroleum-based chemicals with bio-based ones, synthesis of furfural from biomass-derived xylose attracts much attention in recent days. Conventionally, furfural from xylose has been produced via the utilization of highly corrosive, toxic, and environmentally unfriendly mineral acids such as sulfuric acid or hydrochloric acid. In this study, microwave-assisted biphasic reaction process in the presence of novel bio-based heterogeneous acid catalysts was developed for the eco-benign and effective synthesis of furfural from xylose. The microwave was irradiated for reaction acceleration and a biphasic system consisting of $H_2O$ : MIBK (1 : 2) was designed for continuous extraction of furfural into the organic phase in order to reduce the undesired side products formed by decomposition/condensation/oligomerization in the acidic aqueous phase. Moreover, sulfonated amorphous carbonaceous materials were prepared from wood powder, the most abundant lignocellulosic biomass. The prepared catalysts were characterized by FT-IR, XPS, BET, elemental analysis and they were used as bio-based heterogeneous acid catalysts for the dehydration of xylose into furfural more effectively. For further optimization, the effect of temperature, reaction time, water/organic solvent ratio, and substrate/catalyst ratio on the xylose conversion and furfural yield were investigated and 100% conversion of xylose and 74% yield of furfural was achieved within 5 h at $180^{\circ}C$. The bio-based heterogeneous acid catalysts could be used three times without any significant loss of activity. This greener protocol provides highly selective conversion of xylose to furfural as well as facile isolation of product and bio-based heterogeneous acid catalysts can alternate the environmentally-burdened mineral acids.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3535-3541
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• 2014

Bisphenol A is considered as pollutant, because it is toxic and hazardous to living organisms even at very low concentrations. Biological oxidation used for removing this organic from waste water is not suitable and consequently application of catalytic wet oxidation has been considered as one of the best options for treating bisphenol A. We have developed Fe/SBA-15, Ni/SBA-15 and Fe-Ni/SBA-15 as heterogeneous catalysts using the advanced impregnation method for oxidation of bisphenol A in water. The catalysts were characterized with physico-chemical characterization methods such as, powder X-ray diffraction (PXRD), FT-IR measurements, N2 adsorption-desorption isotherm, thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. This work illustrates activity of the catalysts for heterogeneous catalytic degradation reaction revealed with excellent conversion and recyclability. The degradation products identified were not persistent pollutants. GC-MS analysis identified the products: 2,4-hexadienedioic acid, 2,4-pentadienic acid and isopropanol or acetic acid. The leachability study indicated that the catalysts release very little metals to water. Therefore, the possibility of water contamination through metal leaching was almost negligible.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.128-128
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• 2013

Fabrication of heterogeneous catalysts using Atomic Layer Deposition (ALD) has recently been attracting attention of surface chemists and physicists. In this talk, I will present recent results about structures and chemical activities of various catalysts prepared by ALD, particularly focusing on Ni-based catalysts. Ni has been considered as potential catalysts for $CO_2$ reforming of methane (CRM); however, Ni often undergoes rapid decrease in catalytic activity with time, and therefore, application of Ni as catalysts for CRM has been regarded as difficult so far. Deactivation of Ni catalysts during CRM reaction is from either coke formation on Ni surface or sintering of Ni particles during reaction. Two different strategies have been used for enhancing stability of Ni-based catalysts; $TiO_2$ nanoparticles were deposited on micrometer-size Ni particles by ALD, which turned out to reduce coke formation on Ni surfaces. Ni nanoparticles deposited by ALD on mesoporous silica showed high activity and long-term stability from CRM without coke deposition and sintering during CRM reaction. Ni-based catalysts have been also used for oxidation of toluene, which is one of the most notorious gases responsible for sick-building syndrome. It was shown that onset-temperature of Ni catalysts for toluene oxidation is as low as $120^{\circ}C$. At $250\circ}C$, total oxidation of toluene to $CO_2$ with a 100% conversion was found.

• 산업기술연구
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• 제29권A호
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• pp.89-94
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• 2009

The efficiency of heterogeneous catalysts has been investigated in ozonation process for organic removal. Heterogeneous catalytic ozonation was conducted for the degradation of humic acid in the presence of Granular Activated Carbon or Zeolite as a solid catalyst. And the results were compared to those of ozonation alone and adsorption alone without ozonation. The degradation characteristics of humic acid in each process were examined with the values of pH, TOC, $UV_{254}$ and $COD_{Cr}$.

• 공업화학
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• 제24권3호
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• pp.291-298
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• 2013

공액 리놀레산 메틸에스테르는 불균일계 촉매인 니켈 담지 제올라이트계 촉매를 이용하여 리놀레산 메틸에스테르의 이성질화를 통해 합성할 수 있다. 니켈 담지 제올라이트계 촉매는 HY 제올라이트로부터 KCl 수용액을 이용해 이온교환하여 KY 제올라이트를 합성한 뒤 함침법을 통해 니켈을 담지하여 합성하였다. 합성된 촉매는 수소를 이용하여 전처리하여 공액화 반응에 사용하였다. 그 결과 낮은 온도에서 HY 촉매는 높은 전환율을 나타내었지만 공액화 반응에 대해 낮은 선택도를 나타내었다. KY 촉매는 낮은 온도에서 상대적으로 낮은 전환율을 나타내었으나 높은 온도에서 HY 촉매와 유사한 전환율을 보였으며, 낮은 온도에서도 공액화 반응에 대해 높은 선택도를 나타내었다. 결과적으로 반응 온도 $220^{\circ}C$에서 4 wt% Ni/KY720을 이용하여 가장 높은 63.4%의 수율을 얻었다.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.403-408
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• 2012

In this study, the homogenous Pd nanoparticles (Pd NPs) were first prepared with bayberry tannin (BT) as the stabilizers. Subsequently, the obtained bayberry tannin-stabilized Pd nanoparticles (BT-Pd) were immobilized onto ${\gamma}-Al_2O_3$ to prepare heterogeneous ${\gamma}-Al_2O_3$-BT-Pd catalysts. Fourier Transformation Infrared Spectrum (FTIR) and X-ray Photoelectron Spectroscopy (XPS) analyses confirmed that the Pd NPs were well stabilized by the phenolic hydroxyl groups of BT. Transmission Electron Microscopy (TEM) observation indicated that the diameter of the Pd NPs can be effectively controlled in the range of 4.2-16.0 nm by varying the amount of BT. It is found that the ${\gamma}-Al_2O_3$-BT-Pd catalysts exhibit highly activity for various olefin hydrogenations. For example, the initial TOF (turnover frequency) of the ${\gamma}-Al_2O_3$-BT-Pd in the allyl alcohol hydrogenation is as high as $12804 mol{\cdot}mol^{-1}{\cdot}h^{-1}$. Furthermore, the ${\gamma}-Al_2O_3$-BT-Pd can be reused 5 times without significant loss of activity, exhibiting a superior reusability as compared with conventionally prepared ${\gamma}-Al_2O_3$-Pd catalysts.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2748-2752
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• 2012

Cr(III) and Co(III) complexes with acetylacetonate were anchored onto a mesoporous MCM-41 through Schiff condensation. The materials were characterized by XRD, FT-IR, BET, CHN and ICP techniques. Elemental analysis of samples revealed that one C=N bond was formed through Schiff condensation on MCM-41 surface. The catalysts were tested for the alcohol oxidations using t-butyl hydroperoxide (TBHP) and $H_2O_2$ as oxidant. The catalytic experiments were carried out at both room temperature and reflux condition. Various solvents such as dichloromethane, acetonitrile and water were examined in the oxidation of alcohols. Among the different solvents, catalytic activity is found more in acetonitrile. Further, the catalysts were recycled three times in the oxidation of alcohols and no major change in the conversion and selectivity is observed, which shows that the immobilized metal-acetylacetonate complexes are stable under the present reaction conditions.

• Carbon letters
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• 제27권
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• pp.42-49
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• 2018

A citric acid functionalized graphene oxide nanocomposite was successfully synthesized and the structure and morphology of the nanocatalyst were comprehensively characterized by Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, X-ray diffraction patterns, atomic force microscopy images, scanning electron microscopy images, transmission electron microscopy images, and thermogravimetric analysis. The application of this nanocatalyst was exemplified in an important condensation reaction to give imidazole derivatives in high yields and short reaction times at room temperature. The catalyst shows high catalytic activity and could be reused after simple work up and easy purification for at least six cycles without significant loss of activity, which indicates efficient immobilizing of citrate groups on the surface of graphene oxide sheets.

• 한국고분자학회지:고분자과학과기술
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• 제4권3호
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• pp.189-192
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• 1993

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2099-2104
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• 2013

We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.