• Title/Summary/Keyword: Lattice oxygen

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Chemical Doping of $TiO_2$ with Nitrogen and Fluorine and Its Support Effect on Catalytic Activity of CO Oxidation

  • Chakravarthy, G. Kalyan;Kim, Sunmi;Kim, Sang Hoon;Park, Jeong Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.142.2-142.2
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    • 2013
  • The effect of substrate on catalytic activity of CO oxidation with transition metal Platinum nanoparticles on doped and undoped TiO2 was investigated. Titanium dioxide was doped chemically with non-metal anions including nitrogen and fluorine. Undoped TiO2 was synthesized via simple conventional sol-gel route. Thin films of titania were developed by spin coating technique and the characterization techniques SEM, XRD, UV-Vis Absorption Spectroscopy and XPS were carried out to examine the morphology of films, crystal phase, crystallites, optical properties and elemental composition respectively. XPS analysis from doped TiO2 confirmed that the nitrogen site were interstitial whereas fluorine was doped into TiO2 lattice substitutionally. Catalytic activity systems of Pt/doped-TiO2 and Pt/undoped-TiO2 were fabricated to reveal the strong metal-support interaction effect during catalytic activity of CO oxidation reactions. By arc plasma deposition technique, platinum nanoparticles with mean size of 2.7 nm were deposited on the thin films of doped and undoped titanium dioxide. The CO oxidation was performed with 40 Torr CO and 100 Torr O2 with 620 Torr He carrier gas. Turn over frequency was observed two to three folds enhancement in case of Pt/doped TiO2 as compared to Pt/TiO2. The electronic excitation and the oxygen vacancies that were formed with the doping process were the plausible reasons for the enhancement of catalytic activity.

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Fabrication and thermal stability of flower-like CeO2 with high surface area via anisotropic crystallization of carbonate precipitation (탄산염 침전 전구체의 결정 이방성 제어를 통한 고 비표면적 flower-like CeO2 분말의 제조 및 고온 안정성 평가)

  • Kim, Hanbit;Shin, Tae Ho
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.29 no.4
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    • pp.160-166
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    • 2019
  • Cerium oxide ($CeO_2$, often called as Ceria) is one of the valuable rare earth oxide materials, which has been widely used for high temperature applications such as solid oxide fuel cells, automotive three-way catalysts and oxygen storage capacity. Considering those application, it is important to improve high redox and thermal stability with high surface morphology because the high surface area of $CeO_2$ could improve the catalytic reactivity at high temperature conditions. Herein we successfully fabricated hierarchical flower-like $CeO_2$ deposited via controlling pathway of precipitation reaction to supply carbonate ion lead to the flower-like morphology. The hexagonal lattice system of precipitated precursor shows better thermal stability then orthorhombic one during thermal cycling condition.

Simultaneous regulation of photoabsorption and ferromagnetism of NaTaO3 by Fe doping

  • Yang, Huan;Zhang, Liguo;Yu, Lifang;Wang, Fang;Ma, Zhenzhen;Zhou, Jie;Xu, Xiaohong
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1422-1425
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    • 2018
  • $NaTa_{1-x}Fe_xO_3$ ($0{\leq}x{\leq}0.40$) nanocubes were synthesized by a relatively low temperature hydrothermal method, using $Ta_2O_5$, $FeCl_3$ and NaOH as the precursors. The UV-vis diffuse reflectance spectra showed that $NaTa_{1-x}Fe_xO_3$ had significant visible-light-absorbing capability, and the absorption edge of $NaTaO_3$ shifted to longer wavelength with the increase of Fe dopants. Moreover, $NaTa_{1-x}Fe_xO_3$ exhibited room-temperature ferromagnetism when $Fe^{3+}$ occupied $Ta^{5+}$ sites in $NaTaO_3$ crystal lattice. The ferromagnetism is mainly attributed to the superexchange interactions between doped $Fe^{3+}$, rather than the contribution of oxygen vacancies caused by Fe doping. Therefore, Fe doping can simultaneously regulate the optical and magnetic properties of $NaTaO_3$ semiconductor, which will enable its potential applications in multifunctional optical-electronics and opticalspintronics devices.

Effect of Vanadium Loading Amount on Pt/V/TiO2 Catalyst on NH3-SCO Reaction (NH3-SCO 반응에서 Vanadium 담지함량이 Pt/V/TiO2 촉매에 미치는 영향)

  • Kim, Min Su;Kim, Ki Wang;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.33 no.6
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    • pp.594-599
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    • 2022
  • In the study, NH3-SCO (selective catalytic oxidation) reaction activity accodrding to vanadium loading amount were compared when preparing Pt/V/TiO2. Considering both NH3 conversion rate and N2 selectivity, V 2 wt% loading of the catalyst showed the best activity. When the correlation between physical/chemical characteristics and reaction activity was confirmed, it was confirmed that the increase in lattice oxygen and (V3+ + V4+) ratios were active factor. In addition, when the SO2 durability experiment was conducted using the best catalyst, it was confirmed that the influence was insignificant even if the high concentration of SO2 was injected.

Phase Transformation of 2 Components(CaO-, $Y_2O_3$-, MgO-$ZrO_2$) and 3 Components(MgO-$ZrO_2-Al_2O_3)$ Zirconia by X-ray Diffraction and Raman Spectroscopy (X-선회절과 Raman 분광분석을 이용한 2성분계(CaO-, $Y_2O_3$-, MgO-$ZrO_2$) 및 3성분계(MgO-$ZrO_2-Al_2O_3)$ Zirconia의 상전이연구)

  • 은희태;황진명
    • Journal of the Korean Ceramic Society
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    • v.34 no.2
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    • pp.145-156
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    • 1997
  • ZrO2 phase transformations depending on the type and amount of dopants and the sintering temperatures were studied for the 2 components (CaO-, Y2O3-, MgO-ZrO2) and the 3 components(MgO-ZrO2-Al2O3)ZrO2 powder by X-ray diffraction and Raman spectroscopy. In the CaO- and Y2O3-ZrO2 systems, as the CaO and Y2O3 contents increased to 6~15mol% and 3~15mol% respectively, we were not able to identify between tetragonal and cubic in the X-ray diffraction patterns. On the other hand, all Raman modes shifted to lower wavenumbers, decreasing in intensity and the number of bands, markedly. These phenomena were caused by tetragonallongrightarrowcubic phase transformation and interpreted by the breakdown of the wave vector selection rule(k=0) and the structural disorder associated with the formation of oxygen sublattice which was caused by the substitution between Zr4+ ion and Ca2+ or Y3+ ion in ZrO2 matrix. The monoclinic to cubic phase transformation occurred in 10mol% MgO-ZrO2 system. As the Al2O3 content increased from 0 to 20mol% in the MgO-ZrO2-Al2O3 systems, cubic phase transformed to monoclinic phase, this is because the MgO didn't play a role in a stabilizer because of the formation of the spinel(MgAl2O4) by the reaction between MgO and Al2O3, Also, the ZrO2 phase transformation was explained by the change of it's lattice parameters depending on the type and amount of dopants. Namely, as the amount of dopant increased to 10~13mol%, the axial ra-tio c/a came close to unity with increasing the lattice parameter a and decreasing the lattice parameter c. At that time, the tetragonallongrightarrowcubic phase transformation occurred.

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Comparison of Pretreatment Method for the Enhancement of CO2 Mineralogied Sequestration using by Serpentine (이산화탄소 광물고정화 효율 증진을 위한 사문석의 전처리 방법의 비교)

  • Jang, Na-Hyung;Park, Sung-Kwon;Shim, Hyun-Min;Kim, Hyung-Taek
    • Applied Chemistry for Engineering
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    • v.21 no.1
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    • pp.24-28
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    • 2010
  • Since the reaction of mineral fixation proceeds with a very slow rate, the pretreatment method to increases the rate of carbonation reaction should be required. To increase the reactivity of serpentine with $CO_{2}$, two pretreatment methods are performed in this study. The heat treatment is done at $630^{\circ}C$. A heat-treated serpentine shows that the strength of -OH has a lower peak in FT-IR spectrum. Chemical pretreatment is the method of leaching of magnesium from serpentine using sulfuric acid at $75^{\circ}C$ for 1 h. Because the protonation of the oxygen atoms polarizes and weakens the Mg-O-Si bond, the removal of magnesium atoms from the crystal lattice was facilitated. After performing the pre-treatment of serpentine, $CO_{2}$ fixation experiments are performed with treated serpentine in the batch reactor. Heat-treated serpentine is converted into 43% magnesite conversion, whereas untreated serpentine has 27% of magnesite conversion. Although the results of the heat-pretreatment are encouraging, this method is prohibited due to excessive energy consumption. Furthermore chemical pretreatment serpentine routes have been proposed in an effort to avoid the cost prohibitive heat pretreatment, in which the carbonation reaction was conducted at 45 atm and $25^{\circ}C$. Chemical-treated serpentine, in particularly is corresponded to a conversion of 42% of magnesite compared to 24% for the un-treated serpentine.

Study of Nonstoichiometry and Physical Properties of the Mixed Valency $Sr_xEu_{1-x}FeO_{3-y}$ ($0.00{\leq}x{\leq}$1.00) System (혼합원자가 $Sr_xEu_{1-x}FeO_{3-y}$ ($0.00{\leq}x{\leq}$1.00)계의 비화학량론과 물성 연구)

  • Ji Young Min;Kwon Sun Roh;Chul Hyun Yo
    • Journal of the Korean Chemical Society
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    • v.38 no.12
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    • pp.873-879
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    • 1994
  • A series of samples of solid solutions in the $Sr_xEu_{1-x}FeO_{3-y}(0.00{\leq}x{\leq}1.00)$ system has been prepared at $1200^{\circ}C$ under an atmospheric air pressure. The structures of solid solutions are studied by X-ray diffraction, thermal, Mohr salt, and Mossbauer spectroscopic analyses. Their physical properties are also discussed with the electrical conductivities. X-ray diffraction data for the compositions of x = 0.00, 0.25, and 1.00 are assigned to the orthorhombic and the compositions of x = 0.50 and 0.75 to the cubic systems. The lattice volume reduced to cubic cell increases with the x value. The mole ratio of $Fe^{4+}$ iometric chemical formulas of the system are formulated from the x, $\tau$, and y values. The mixed valency state of Fe ions, the oxygen coordination, and covalent bond character are discussed with the Mossbauer spectroscopic data. The activation enegy of the electrical conductivities depends on the $\tau$ value in the temperature range of -$100^{\circ}C$ to $600\circC$ under the air pressure. The Mossbauer spectrum and electrical conductivity of the solid solutions are discussed with nonstoichiometric chemical compositions.

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Effects of $Y_2O_3$ addition and sintering time on denazification and thermal conductivity of AlN ceramics during hot-press sintering ($Y_2O_3$ 첨가와 소결 시간이 AlN 세라믹스의 일축 가압 소결 거동 및 열전도도에 미치는 영향)

  • Chae, Jae-Hong;Park, Joo-Seok;Ahn, Jong-Pil;Kim, Kyoung-Hun;Lee, Byung-Ha
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.18 no.6
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    • pp.237-241
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    • 2008
  • Hot-press sintering of AlN ceramics were carried out with $Y_2O_3$ as sintering additive at a sintering temperature $1,750{\sim}1,850^{\circ}C$. The effect of $Y_2O_3$ addition and sintering time on sintering behavior and thermal conductivity of AlN ceramics was investigated. $Y_2O_3$ added AlN showed noticeably higher denazification rate than pure AlN. The thermal conductivity of AlN specimens was promoted by the addition of $Y_2O_3$ in spite of the formation of YAG secondary phase in AlN grain boundaries and grain boundary triple junction because $Y_2O_3$ addition could reduced the oxygen contents in AlN lattice which is primary factor of thermal conductivity. Typically, the thermal conductivity of 5 wt% $Y_2O_3$ added specimen was dramatically improved by the increase of sintering time because the elimination of YAG secondary phases from the grain boundary due to the evaporation, as well as the grain-growth of AlN grains.

Characteristics of Nano-structured SiO2:Zn Hollow Powders Prepared in the Micro Drop Fluidized Reactor (MDFR) Process (미세액적 유동반응기 공정에서 연속제조된 나노구조 SiO2:Zn 원환형 입자의 특성)

  • Yang, Si Woo;Kang, Yong;Kang, Ho
    • Korean Chemical Engineering Research
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    • v.56 no.4
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    • pp.585-591
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    • 2018
  • Characteristics of nano-structured $SiO_2:Zn$ hollow powders prepared in the micro drop fluidized reactor process were investigated with respect to bandgap energy and surface activity. The $SiO_2:Zn$ hollow powders were successfully prepared continuously in the one step process with reasonable production efficiency, with varying the amount of THAM (tris(hydroxymethyl)-aminomethane) additive and concentration of $Zn^{2+}$ ions. The doping of $Zn^{2+}$ ions into $SiO_2$ lattice led to the reduction of bandgap energy by forming the acceptor level of $Zn^{2+}$ below the conduction band of $Si^{4+}$ ions. The hollow shape also contributed to reduce the bandgap energy of $SiO_2:Zn$ powders. The doping of $Zn^{2+}$ ions into $SiO_2$ hollow powders could enhance the surface activity by forming SiO-H stretching and oxygen vacancies at the surface of $SiO_2:Zn$ powders.

The Effect of Trivalent Cation Doping on the Low Temperature Phase Stability of 2Y-TZP (3가 양이온 산화물이 첨가된 2Y-TZP의 저온 상안정성)

  • Jang, Ju-Woong;Kim, Hak-Kwan;Lee, Deuk-Yong;Kim, Dae-Joon;Park, Sun-Min
    • Journal of the Korean Ceramic Society
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    • v.39 no.11
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    • pp.1055-1062
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    • 2002
  • The phase stability and the Low Temperature Degradation(LTD) mechanism of Tetragonal Zirconia Polycrystals(TZP), sintered specimens of $Y_2O_3$-Stabilized Zirconia(2Y-TZP), doped with trivalent cations, were evaluated by investigating meachnical properties, Raman spectra, lattice parameter variation and the oxygen vacancy behavior under applied electric field. XRD observation was put forward on 2Y-TZP doped with trivalent cation whose ionic radii were larger than $Zr^{4+}(Sc^{3+},\;Yb^{3+},\;Y^{3+},\;Sm^{3+},\;Nd^{3+},\;La^{3+})$ up to 2 mol% and sintered at 1500 h for 1h. For $La^{3+}$ doping, the stability of tetragonal phase was degraded due to the formation of the pyrochlore phase $(La_2Zr_2O_7)$ as the dopant content increased above exceeded 0.5 mol%. As the dosage increased, tetragonal phase maintained for the case of $Sc^{3+}$, whose radius was similar to $Zr^{4+}$, on the other hand, the cubic phase was formed for the cases of $Yb^{3+},\;Y^{3+},\;Sm^{3+},\;Nd^{3+}$. As the radii of dopant cation increased, c/a ratio increased and it was experimentally observed that the amount of monoclinic phase decreased when the specimens were annealed at $220{\circ}C$ for 500 h.