• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.1989-1996
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• 2006

The $NiSO_4/CeO_2-ZrO_2 $catalysts containing different nickel sulfate and $CeO_2$ contents were prepared by the impregnation method, where support, $CeO_2-ZrO_2$was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and cerium nitrate solution followed by adding an aqueous ammonia solution. No diffraction line of nickel sulfate was observed up to 20 wt %, indicating good dispersion of nickel sulfate on the surface of $CeO_2-ZrO_2$. The addition of nickel sulfate (or $CeO_2$) to $ZrO_2$ shifted the phase transition of $ZrO_2$ from amorphous to tetragonal to higher temperatures because of the interaction between nickel sulfate (or $CeO_2$) and $ZrO_2$. A catalyst (10-$NiSO_4/1-CeO_2-ZrO_2$) containing 10 wt % $NiSO_4$ and 1 mole % $CeO_2$, and calcined at $600{^{\circ}C}$ exhibited a maximum catalytic activity for ethylene dimerization. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The role of $CeO_2$was to form a thermally stable solid solution with zirconia and consequently to give high surface area, thermal stability and acidity of the sample.

• 대한전기학회:학술대회논문집
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• 대한전기학회 2001년도 하계학술대회 논문집 C
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• pp.1414-1416
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• 2001

Crack-free and homogeneous compact and epitaxial lead zirconate titanate(PZT) ferroelectric thin films with perovsikte structure have been prepared by sol-eel method. Tetrabutyl titanate, lead acetate and zirconium nitrate are used as raw materials. Glacial acetic acid is used as a catalyst. Ethylene glycol monoethyl ether is used as a solvent. The annealing temperatures of th thin films are 600~900$^{\circ}C$. The values of the remanent polarization Pr, and the coercive field $E_c$, of the PZT ceramic thin films are 46, 35 ${\mu}C/cm^2$ respectively.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.241.1-241.1
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• 2011

Numerous possible applications for $ZrO_2$ nanotubes exist such as for catalyst support structures, for sensing or for applications as a solid state electrolyte. Especially, because of a large specific surface area, high efficiency for solid oxide fuel cell (SOFC) application at low temperature can be expected for nanotublar structures in even small size. A zirconium precursor, Tetrakis (ethylmethylamino) zirconium, TEMAZr and $H_2O$ oxidant were used to deposit$ZrO_2$ thin films on an anodized aluminum oxide (AAO) templates having sub-100nm cylindrical pores by atomic layer deposition (ALD) in the temperature range of 150~250$^{\circ}C$. The crystalline structures of as-prepared and post-annealed $ZrO_2$ nanotubes were characterized by x-ray diffraction and high-resolution transmission electron microscopy. The as-prepared samples at $150^{\circ}C$ and $200^{\circ}C$ were showed amorphous, whereas a mixed phase of tetragonal, monoclinic and amorphous polymorph was observed at $250^{\circ}C$. In the bulk, zirconia remains monoclinic phase up to $1,175^{\circ}C$, however, $ZrO_2$ nanotubes were showed tetragonal phase upon post thermal treatments merely at $400^{\circ}C$. This trend may be indicative of high-curvature surfaces of nanotubes and thereby the presence of intrinsic compressive strain. The amount of amorphous structures in the mixed phase as well as as-grown $ZrO_2$ nanotubes were also gradually decreased by subsequent heat treatment.

• 한국세라믹학회지
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• 제47권4호
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• pp.343-352
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• 2010

A zirconia gel/polymer hybrid nanofiber was produced in a nonwoven fabric mode by electrospinning a sol derived from hydrolysis of zirconium butoxide with a polyvinyl butyral. Results indicated that the hydroxyl groups on the vinyl alcohol units in the backbone of the polymer were involved in the hydrolysis as well as grafting the hydrolyzed zirconium butoxide. In addition, use of acetic acid as a catalyst resulted in further hydrolysis and condensation in the sol, which led to the growth of -Zr-O-Zr- networks among the polymer chains. These networks gradually transformed into a crystalline zirconia structure upon heating. The as-spun fiber was smooth but partially wrinkled on the surface. The average fiber diameter was $690{\pm}110\;nm$. The fiber exhibited a strong but broad blue photoluminescence with its maximum intensity at a wavelength of ~410 nm at room temperature. When the fiber was heat-treated at $400^{\circ}C$, the fiber diameter shrunk to $250{\pm}60\;nm$. Nanocrystals which belonged to a tetragonal zirconia phase and were ~5 nm in size appeared. A strong white photoluminescence was observed in this fiber. This suggests that oxygen or carbon defects associated with the formation of the nanocrystals play a role in generating the photoluminescence. Further heating to $800^{\circ}C$ resulted in a monoclinic phase beginning to form In the heat-treated fibers, coloring occurred but varied depending on the heating temperature. Crystallization, coloring, and phase transition to the monoclinic structure influenced the photoluminescence. At $600^{\circ}C$, the fiber appeared to be fully crystallized to a tetragonal zirconia phase.

• Bulletin of the Korean Chemical Society
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• 제26권11호
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• pp.1749-1756
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• 2005

The $NiSO_4$ supported on FeO-promoted $ZrO_2$ catalysts were prepared by the impregnation method. FeOpromoted $ZrO_2$ was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and iron nitrate solution followed by adding an aqueous ammonia solution. The addition of nickel sulfate (or FeO) to $ZrO_2$ shifted the phase transition of $ZrO_2$ (from amorphous to tetragonal) to higher temperatures because of the interaction between nickel sulfate (or FeO) and $ZrO_2$. 10-$NiSO_4$/5-FeO-$ZrO_2$ containing 10 wt % $NiSO_4$ and 5 mol % FeO, and calcined at 500 ${^{\circ}C}$ exhibited a maximum catalytic activity for ethylene dimerization. $NiSO_4$/FeO-$ZrO_2$ catalysts was very effective for ethylene dimerization even at room temperature, but FeO-$ZrO_2$ without $NiSO_4$ did not exhibit any catalytic activity at all. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The addition of FeO up to 5 mol % enhanced the acidity, surface area, thermal property, and catalytic activities of catalysts gradually, due to the interaction between FeO and $ZrO_2$ and due to consequent formation of Fe-O-Zr bond.

• Korean Chemical Engineering Research
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• 제51권2호
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• pp.208-213
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• 2013

염화 지르코니움산화물을 수용액상하에 $100^{\circ}C$에서 다양한 숙성 시간 동안 환류시켜 지르코니움 수화물을 제조하였고 결정성 $ZrO_2$를 얻기 위하여 $700^{\circ}C$에서 6시간 소성하였다. 제조된 물질의 특성분석을 위하여 시차 열분석, X-선회절 분석, 비표면적과 세공분포 측정, 투과 전자 현미경 분석, 암모니아 승온 탈착 분석, 이산화탄소 승온 탈착 분석 그리고 이소프로판올 승온 탈착 분석을 수행하였다. 24시간 숙성시키고 $700^{\circ}C$에서 소성 후 순수한 정방형계 지르코니아만을 얻을 수 있었다. 숙성시간 증가는 상대적으로 더 작은 입자, 고비표면적 및 고 기공부피의 지르코니아를 제조할 수 있었다. 지르코니아의 숙성 시간이 길어질수록 흡착된 암모니아의 양이 상대적으로 증가하는 경향을 보였고 상대적으로 흡착된 이산화탄소의 양은 감소하였다. 지르코니아 촉매상에서 프로필렌을 생성하는 이소프로판올 탈수 반응에서 촉매 활성은 168시간 동안 숙성하여 제조한 지르코니아 촉매가 가장 좋은 활성이 나타냈다. 이러한 촉매활성은 촉매의 비표면적, 산점, 상대적으로 용이한 프로판올의 탈착과 연관시킬 수 있었다.

• Macromolecular Research
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• 제10권2호
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• pp.97-102
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• 2002

The mixtures of non-conjugated dienes, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (MHD), were successfully synthesized by the reaction of isoprene with ethylene using Fe(III)-based catalyst in toluene. The conversion was over 96 mol% on the basis of the initial amount of isoprene used. The production yield for MHD was nearly 50 mol%, the other was polyisoprene. The mixtures were successfully copolymerized with ethylene by using zirconium-based metallocenes. The products were characterized by the combinations of gas chromatography, high temperature gel permeation chromatography, $^1$H NMR, $^{13}$ C NMR, high temperature $^1$H NMR, UV/visible spectroscopy, and differential scanning calorimetry. It was found that 5-methyl-1,4-hexadiene was active enough to be incorporated into the copolymer chain but the corresponding isomeric material,4-methyl-1,4-hexadiene, was inactive in metallocene-catalyzed copolymerizations. Specifically, in the zirconocene-catalyzed copolymerizations of ethylene with MHD, ansa-structure catalysts seem to be more efficient than non-bridged type zirconocene. The degree of incorporation of MHD in the resulting copolymers was able to be controlled by the amount of non-conjugated dienes used initially.

• 한국재료학회지
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• 제13권2호
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• pp.115-119
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• 2003

The thick film type sensor having Pt/Na Super Ionic Conductor(NASICON) solid electrolyte/Pt/$Na_2$$SO_4$/Pt catalyst system for $SO_2$gas was fabricated by screen-print method. The phase of Na Super Ionic Conductor solid electrolyte sintered at different temperature of 1050, 1150,$ 1250^{\circ}C$ and for different time of 1.5, 2.5, 3.5 hr were investigated by XRD. The Electromotive Force variation of the sensor with $SO_2$concentrations and operating temperatures were investigated. The major phase of Na Super Ionic Conductor film sintered at 115$0^{\circ}C$ for 3.5 hr was sodium zirconium silicon phosphate($Na_3$Zr$_2$$Si_2$PO$_{12}$). The Nernst's slope of Na Super Ionic Conductor sensor for $SO_2$gas with the variation of concentration from 10 to 100 ppm was 167.14 ㎷/decade at the operating temperature of $500 ^{\circ}C$. The increase of oxygen partial pressure was not affected to the variation of Nernst's slope.e.

• 공업화학
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• 제7권5호
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• pp.1006-1014
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• 1996

에틸렌 이량화반응을 위한 일련의 $NiO-ZrO_2/WO_3$촉매를 염화니켈-옥시염화 질코니움 수용액을 공침시키고 ammonium metatungstate용액으로 함침시킨 다음 공기 중에서 소성하여 제조하였다. X-선 회절과 DSC로부터 얻은 결과를 근거로 하면 $ZrO_2$에 NiO 및 $WO_3$를 첨가하면 $ZrO_2$와 첨가된 산화물과의 상호작용으로 $ZrO_2$의 무정형에서 tetragonal phase로의 상전이 온도가 더 높은 온도로 이동되었다. $WO_3$가 첨가되지 않은 $NiO-ZrO_2$는 에틸렌 이량화반응에 전혀 촉매 활성을 나타내지 아니하였으나 $WO_3$가 첨가된 $NiO-ZrO_2/WO_3$촉매는 실온에서도 높은 활성을 나타내었다. 이와 같은 $NiO-ZrO_2/WO_3$의 높은 촉매활성은 $WO_3$의 유도효과에 의한 산세기의 증가와 밀접한 관련이 있었다.

• 한국결정성장학회지
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• 제27권6호
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• pp.309-312
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• 2017

세리아 분말은 Ce 이온의 산화, 환원 반응을 통한 산소저장능력(OSC)이 뛰어나 배기가스를 정화하는 자동차의 삼원촉매에 대표적인 재료로 사용된다. 그러나 일반적으로 세리아는 고온에서 열적 안정성이 떨어지기 때문에 금속이온을 도핑시켜 열적 안정성을 향상시켜 사용한다. 따라서 본 연구에서는 Zr 이온을 세리아 분말에 도핑시켰고, 도핑으로 인해 입자크기가 감소하면서 비 표면적 증가로 인해 그 특성은 더욱 향상되었다. 그리고 본 연구에서는 세리아 및 Zr 이온이 도핑된 세리아를 나노 크기로 합성하기 위해 수열반응법을 이용하여 합성하였다. 수열합성 조건은 pH = 11, 반응온도는 $200^{\circ}C$에서 6시간 동안 합성하였다. 수열합성법을 이용하여 합성된 세리아 및 Zr 도핑 $CeO_2$ 나노 분말의 평균 입자 크기는 약 20 nm 이하였다. 합성된 세리아 나노분말의 비표면적은 $52.03m^2/g$, Zr 이온이 도핑된 $CeO_2$ 분말의 비 표면적 $132.27m^2/g$이었다.