• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1844-1850
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• 2006

Two types of catalyst samples were prepared, one sulfated zirconia and the other silica doped sulfated zirconia. The acidity tests indicate that sulfated zirconia doped with silica has higher concentration and strength of acidic catalyst sites than undoped sulfated zirconia. The acidic surface sites have been characterized using FTIR, NMR, pyridine adsorption, TPD, XRD and nitrogen adsorption. Doping with silica increased the concentration of surface Lewis and Brfnsted acid sites and resulted in generation of proximate acid sites.The activity test indicates that doping sulfated zirconia with silica increases both the acidity and catalytic activity for liquid phase dehydration of methanol at 413-453 K. Methanol is sequentially dehydrated to dimethyl ether and ethylene over both catalysts. Significant amounts of propylene are also formed over the silica-doped catalyst, but not over the undoped catalyst.

• Bulletin of the Korean Chemical Society
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• v.25 no.9
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• pp.1355-1360
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• 2004

The oxidative decomposition of trichloroethylene (TCE) was investigated using palladium catalysts supported on pure and sulfated zirconia. The reactions were performed under dry and wet conditions in the temperature between 200 and $550^{\circ}C$ keeping GHSV of 14,000 $h^{-1}.$ The products such as $C_2Cl_4,\;C_2HCl_5,\;CO\;and\;CO_2$ were observed in the reaction. The addition of water in the feed affected the distribution of reaction product with dramatically improved catalytic activity. The spectroscopic investigations gave an evidence that the strong acid sites play an important role on controlling the catalytic activity. Among the catalysts investigated, the Pd-loaded sulfated zirconia catalyst with 1 wt% Pd was found to exhibit the highest catalytic activity in the presence of water vapor having the stability for 30 h of the reaction at $500^{\circ}C$. The successful performance of the catalyst might be attributed to promotional effect of Pd active sites and strong acid sites induced from surface sulfate species on zirconia.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1809-1813
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• 2013

Sulfated ${\beta}$-cyclodextrin (SCD)-coated zirconia monolith was used as the chiral stationary phase in capillary electrochromatography for enantiomeric separation of basic chiral compounds. SCD adsorbed on the zirconia surface provided a stable chiral stationary phase in reversed-phase eluents. Retention, chiral selectivity and resolution of a set of six basic chiral compounds were measured in eluents of varying pH, composition of methanol and buffer. Optimum mobile phase condition for the separation of the compounds was found to be methanol content of 30%, buffer concentration of 30 mM and pH of 4.0.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.524-528
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• 2012

A kind of nanosized sulfated zirconia was prepared by a hydrothermal method, and full characterized by XRD, TEM, BET, TGA, and FTIR. Its catalytic activity was evaluated in the esterification reactions, including the testing of the catalytic reusability and the optimization of reaction conditions. The obtained catalyst was revealed to be highly efficient solid catalyst for the esterification of acetic acid with n-butanol, presenting the advantages of high conversion and selectivity, easy recovery, and steady reusability.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1659-1664
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• 2014

A porous metal-organic framework (MOF), MIL-101, was synthesized in the presence of sulfated zirconia (SZ) to produce acidic SZ/MIL-101 composites for the first time. The composites were characterized with XRD, nitrogen adsorption, FT-IR, scanning electron microscope, chemical analysis and so on. The composites (SZ/MIL-101s) were successfully applied in a liquid-phase esterification for a high yield of ester. This catalytic result of SZ/MIL-101, compared with that of pure SZ or MIL-101 (showing a negligible yield of ester), suggests that the SZ in the composite is highly active in the acid catalysis probably because of the well-dispersed active species of SZ. Moreover, the esterification is catalyzed in heterogeneous mode as confirmed by negligible esterification after filtration of the catalyst. Finally, microwaves can be efficiently applied both in the synthesis of the composites and the esterification reaction to accelerate the two processes of synthesis and esterification by about 5 times.

• Membrane Journal
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• v.21 no.1
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• pp.30-38
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• 2011

Composite membranes based on sulfonated poly(aryl ether) sulfone (SPAES) with different sulfated zirconia nanoparticles ($s-ZrO_2$) ratio are synthesized and investigated for the improvement of the hydration and the proton conductivity at high temperature and no humidification for fuel cell applications. X-ray diffraction technique is employed to characterize the structure and the size of $s-ZrO_2$ nanoparticles. The sulfation effect of $s-ZrO_2$ nanoparticles is verified by FT-IR analysis. The properties of the SPAES composite membranes with the various $s-ZrO_2$ ratio are evaluated by ion exchange capacity and water content. The proton conductivities of the composite membranes are estimated at room temperature with full hydration and at the various high temperature without external humidification. The composite membrane with 5 wt% $s-ZrO_2$ shows the highest proton conductivity. The proton conductivities are $0.9292\;S\;cm^{-1}$ at room temperature with full hydration and $0.0018\;S\;cm^{-1}$ at $120^{\circ}C$ without external humidification, respectively.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.108.2-108.2
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• 2011

This presentation shows energy-efficiency of microwave-accelerated esterification of free fatty acid with a heterogeneous catalyst by net microwave power measurement. In the reaction condition of 5wt% sulfated zirconia and 1:20 molar ratio of oil to methanol at $60^{\circ}C$ and atmospheric pressure, more than 90% conversion of the esterification was achieved in 20 minutes by microwave heating, while it took about 130 minutes by conventional heating. Electric energy consumption for the microwave heating in this accelerated esterification was only 67% of estimated minimum heat energy demand because of significantly reduced reaction time.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.135.1-135.1
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• 2010

최근 고온에서 사용 가능한 PEMFC용 고분자전해질 막 개발에 대한 연구가 활발히 진행되고 있다. PEMFC가 고온에서 작동하게 되면 높은 성능과 많은 장점을 갖게 된다. PEMFC를 $100^{\circ}C$ 이상에서 운전하게 될 경우 백금 전극 반응을 향상시켜 고가의 백금 촉매 양을 줄일 수 있게 되고, 수소연료 속에 미량 포함된 CO에 의한 촉매표면 피독현상에 대한 내구성을 높일 수 있어 저 순도 수소연료 사용이 가능해 진다. 또한 가습장치와 수소 연료 개질장치의 부피를 줄일 수 있게 되어 전체적인 PEMFC 시스템이 단순화 된다. 현재 연료전지용 고분자 전해질막으로 DuPont사의 과-불소계 고분자 전해질막인 Nafion$^{(R)}$이 가장 널리 사용되고 있다. Nafion$^{(R)}$은 유연한 분자구조 안에 소수성이 강한 주사슬과 친수성을 나타내는 술폰산이 결합된 곁사슬이 존재하여 술폰화 곁사슬의 클러스터 둘레에는 친수성 영역이 형성이 되기때문에 소수/친수 상 분리가 잘되어 이온 클러스터 형성이 용이하지만 제조비용이 높은 단점을 갖고 있다. 특히, 전해질 막내에서 Bronsted base 역할을 하는 물에 의해 이온전도가 이루어지기 때문에 고온에서는 수분증발로 인해 성능이 급격히 감소된다. 따라서, 본 연구에서는 고온 저가습 조건에서 운전이 가능하고 Nafion이 갖는 문제점을 해결하고자, 내열특성이 뛰어나며 높은 수소이온 전도도 학보가 용이한 Sulfonated Poly(aryl ether)sulfone(SPAES) 고분자 전해질에, 고온에서도 수화성이 유지될 수 있도록 지르코니아를 황산화한 sulfated zirconia(s-$ZrO_2$)를 함침하여 복합 고분자전해질막을 제조하여 고온 저가습 조건에서의 수소이온 전도 특성에 관한 연구를 수행하였다. 개발된 막의 물리/화학적 특성은 water content(Wup%), 이온교환 용량(IEC, meq $g^{-1}$), 수소이온전도도(s $cm^{-1}$) 열 중량 분석(TGA), X선 회절분석(XRD) 등을 통하여 분석 및 관찰하였다. 내화학 및 열적 특성분석 결과, 황산화 반응공정으로 $ZrO_2$에 술폰산기가 안정적으로 결합하고 있음이 관찰되었으며, 본 연구에서 개발된 유 무기 복합막이 $250^{\circ}C$이상 열적안정성을 확보하고 있는 것으로 판단되었다. $100^{\circ}C$ 이하의 저온 영역에서, 일정 비율의 s-$ZrO_2$/SPAES막에서 이온교환용량(IEC)이 순수 SPAES 막보다 낮음에도 불구하고, water uptake가 증가함과 동시에 수소이온 전도도가 향상된 것을 관찰하였다. 또한, 고온에서는 수소이온이 자유롭게 이동할 수 있는 water channel을 형성하는 free water는 증발 하지만 s-$ZrO_2$와 SPAES의 술폰산기 사이에 강력하게 결합하고 있는 bound Water는 $100^{\circ}C$ 이상의 고온 영역에서도 존재하여, 비록 무가습 조건에서도 일정 비율의 s-$ZrO_2$/SPAES50 전해질 막의 경우, 높은 전도도를 나타냄을 관찰할 수 있었다. 따라서 본 연구를 통해 저가습 고온 적용을 목적으로 개발된 s-$ZrO_2$/SPAES50막은 우수한 내열 특성을 나타냄과 동시에 저가습 고온 영역($120^{\circ}C$, $50RH{\downarrow}$)에서 높은 수소이온 전도도를 유지하여, 고온 저가습 연료전지 운전에 적합할 것으로 사료된다.

• Applied Chemistry for Engineering
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• v.25 no.3
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• pp.254-261
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• 2014

The transformer is a static electrical device that transfers energy by inductive coupling. Then, heat is occurred at coils, inner transformer was filled with insulating oils for cooling and insulation. Although mineral oil as insulating oil has been widely used, it does not meet health and current environmental laws because it is not biodegradable. Therefore, in this study, the diglycerol ester was synthesized with diglycerol and fatty acids (oleic acid and caprylic acid) over various catalysts for insulating oil having biodegradability, high flash points and low pour points. The sulfated zirconia ($SO_4{^{2-}}/ZrO_2$) catalyst prepared at different calcination temperature shows the highest conversion of fatty acids at $600^{\circ}C$ due to crystallinity and high density of acid sites per surface area. When the molar ratio of oleic acid and caprylic acid is 1:3, the diglycerol ester shows superior insulation properties that are the flash point of $306^{\circ}C$ and pour point of $-50^{\circ}C$. The insulation properties of synthesized diglycerol ester shows the pour point of $-50^{\circ}C$ and the flash point of over $300^{\circ}C$. Therefore, diglycerol ester is superior to the vegetable oils in insulation properties.