• Title/Summary/Keyword: Doping

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Effects of Mn- and K-addition on Catalytic Activity of Calcium Oxide for Methane Activation (메탄 활성화반응에서 산화칼슘 촉매의 활성에 대한 망간과 칼륨의 첨가효과)

  • Park, Jong Sik;Kong, Jang Il;Jun, Jong Ho;Lee, Sung Han
    • Journal of the Korean Chemical Society
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    • v.42 no.6
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    • pp.618-628
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    • 1998
  • Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800$^{\circ}C$ to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction(XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally $p(CH_4)/p(O_2)=250$ Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best $C_2$ yield of 8.0% with a selectivity of 43.2% at 775$^{\circ}C$. The $C_2$ selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO([Mn] > 6.3 mol%) catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the $C_2$ selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000$^{\circ}C$ at Po2's of $10^{-3}\; to\;10^{-1}\;atm.$ The electrical conductivity was decreased with Mn-doping and increased with increasing $P0_2$in the range of $10^{-3}\;to\;10^{-1}\;atm,$ indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry.

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The Photovoltaic Effect of Iodine-Doped Metal Free Phthalocyanine/ZnO System (Ⅰ) (요오드가 도핑된 무금속 프탈로시아닌/산화아연계의 광기전력 효과(Ⅰ))

  • Heur, Soun-Ok;Kim, Young-Soon;Park, Yoon-Chang
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.163-175
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    • 1995
  • Metal free phthalocyanine($H_2Pc$) partially doped with iodine, $H_2Pc(I)x$, has been made to improve photosensitizing efficiency of ZnO/$H_2Pc$. The content of iodine dopant level(x) for $H_2Pc(I)x$ upon $H_2Pc$ polymorphs was characterized as ${\chi}-H_2Pc(I)_{0.92}$ and ${\beta}-H_2Pc(I)_{0.96}$ by elemental analysis. Characterization of iodine-oxidized $H_2Pc$ were investigated by TGA (thermogravimetric analysis), UV-Vis, FT-IR, Raman and ESR (electron spin resonance) spectrum, and the adsorption properties of $H_2Pc(I)x$ on ZnO were characterized by means of Raman and ESR studies. TGA for $H_2Pc(I)x$ showed a complete loss of iodine at approximately 265$^{\circ}C$ and the Raman spectrum of $H_2Pc(I)x$ and ZnO/$H_2Pc(I)x$ at 514.5 nm showed characteristic $I_3^-$ patterns in the frequency region 90∼550 $cm^{-1}$. ZnO/$H_2Pc(I)x$ exhibited a very intense and narrow ESR signal at $g=2.0025{\pm}0.0005$ compared to $H_2Pc$/ZnO. Iodine doped ZnO/$H_2Pc(I)x$ showed a better photosensitivity compared to iodine undoped ZnO/$H_2Pc$. That is, the surface photovoltage of ${\chi}-H_2Pc(I)_{0.92}$/ZnO was approximately 31 times greater than that of ZnO/${\chi}-H_2Pc$ and ZnO/${\beta}-H_2Pc(I)_{0.96}$ was 5 times more efficient than ZnO/${\beta}-H_2Pc$ at 670 nm. And the dependence of photosensitizing effect upon $H_2Pc$ polymorphs was exhibited that the surface photovoltage of ZnO/${\chi}-H_2Pc(I)_{0.92}$ was approximately 5 times greater than ZnO/${\beta}-H_2Pc(I)_{0.96}$ at 670 nm. Therefore Iodine doping of H_2Pc$ resulted in increase in photoconductivity of $H_2Pc$ and photovoltaic effect of ZnO/$H_2Pc$ in the visible region.

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The biofilm removal effect of MnO2-diatom microbubbler from the dental prosthetic surfaces: In vitro study (치과 보철 재료 표면에서 MnO2-diatom microbubbler의 세균막 제거 효과 연구: In vitro study)

  • Lee, Eun-Hyuk;Seo, Yongbeom;Kwon, Ho-Bum;Yim, Young-Jun;Kong, Hyunjoon;Kim, Myung-Joo
    • The Journal of Korean Academy of Prosthodontics
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    • v.58 no.1
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    • pp.14-22
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    • 2020
  • Purpose: The aim of this study is to evaluate the effectiveness of MnO2-diatom microbubbler (DM) on the surface of prosthetic materials as a mouthwash by comparing the biofilm removal effect with those previously used as a mouthwash in dental clinic. Materials and methods: DM was fabricated by doping manganese dioxide nanosheets to the diatom cylinder surface. Scanning electron microscopy (SEM) was used to observe the morphology of DM and to analyze the composition of doped MnO2. Stereomicroscope was used to observe the reaction of DM in 3% hydrogen peroxide. Non-precious metal alloys, zirconia and resin specimens were prepared to evaluate the effect of biofilm removal on the surface of prosthetic materials. And then Streptococcus mutans and Porphyromonas gingivalis biofilms were formed on the specimens. When 3% hydrogen peroxide solution and DM were treated on the biofilms, the decontamination effect was compared with chlorhexidine gluconate and 3% hydrogen peroxide solution by crystal violet staining. Results: Manganese dioxide was found on the surface of the diatom cylinder, and it was found to produce bubble of oxygen gas when added to 3% hydrogen peroxide. For all materials used in the experiments, biofilms of the DM-treated groups got effectively removed compared to the groups used with chlorhexidine gluconate or 3% hydrogen peroxide alone. Conclusion: MnO2-diatom microbubbler can remove bacterial membranes on the surface of prosthetic materials more effectively than conventional mouthwashes.

Preparation and Oxygen Permeation Properties of La0.07Sr0.3Co0.2Fe0.8O3-δ Membrane (La0.07Sr0.3Co0.2Fe0.8O3-δ 분리막의 제조 및 산소투과 특성)

  • Park, Jung Hoon;Kim, Jong Pyo;Baek, Il Hyun
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.477-483
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    • 2008
  • $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ oxide was synthesized by a citrate method and a typical dense membrane of perovskite oxide has been prepared using as-prepared powder by pressing and sintering at $1300^{\circ}C$. Precursor of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ prepared by citrate method was investigated by TGA and XRD. Metal-citrate complex in precursor was decomposed into perovskite oxide in the temperature range of $260{\sim}410^{\circ}C$ but XRD results showed $SrCO_3$ existed as impurity at less than $900^{\circ}C$. Electrical conductivity of membrane increased with increasing temperature but then decreased over $700^{\circ}C$ in air atmosphere ($Po_2=0.2atm$) and $600^{\circ}C$ in He atmosphere ($Po_2=0.01atm$) respectively due to oxygen loss from the crystal lattice. The oxygen permeation flux increased with increasing temperature and maximum oxygen permeation flux of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ membrane with 1.6 mm thickness was about $0.31cm^3/cm^2{\cdot}min$ at $950^{\circ}C$. The activation energy for oxygen permeation was 88.4 kJ/mol in the temperature range of $750{\sim}950^{\circ}C$. Perovskite structure of membrane was not changed after permeation test of 40 h and the membrane was stable without secondary phase change with 0.3 mol Sr addition.

Crystal Structure and Mossbauer Studies of 57Fe Doped TiO2 (57Fe가 치환된 TiO2의 결정학적 및 뫼스바우어 분광학적 연구)

  • Lee, Hi-Min;Shim, In-Bo;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.13 no.6
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    • pp.237-242
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    • 2003
  • $Ti_{1-x}$$^{57}$ F $e_{x}$ $O_2$(0.0$\leq$x$\leq$0.07) compounds were fabricated using the sol-gel method, and the crystal structure and magnetic properties were investigated as a function of doped $^{57}$ Fe concentration. X-ray diffraction patterns showed a pure anatase single phase, without any segregation of Fe into particulate. With varying $^{57}$ Fe concentration, we could observe unusual magnetic phenomena in these materials. Doping $^{57}$ Fe into the Ti $O_2$ nonmagnetic semiconductor formed magnetic properties, but the gradual increase of $^{57}$ Fe concentration decreased rapidly the ferromagnetic properties rather than enhanced the ferromagnetic properties. Obvious ferromagnetic behavior was shown for the samples with x$\leq$0.01, while paramagnetic behavior was shown for the sample with x$\geq$0.03. These phenomena could be verified using Mossbauer measurement. Separation of the ferromagnetic phase (sextet) and the paramagnetic phase (doublet) of the samples with different $^{57}$ Fe concentration was characterized. Samples with x$\leq$0.01 have sextet and doublet simultaneously, but samples with x$\geq$0.03 have only doublet at room temperature. This indicates that the sample x$\leq$0.01 have the ferromagnetic phase at room temperature. This result corresponded with the M-H loops referenced above and reveals an interesting feature that there is a critical limit of $^{57}$ Fe concentration (0.01$\leq$0.01 samples was fundamentally attributable to the paramagnetic phase as well as the ferromagnetic phase.e.

Structural change and electrical conductivity according to Sr content in Cu-doped LSM (La1-xSrxMn0.8Cu0.2O3) (Sr 함량이 Cu-doped LSM(La1-xSrxMn0.8Cu0.2O3)의 구조적변화와 전기전도도에 미치는 영향)

  • Ryu, Ji-Seung;Noh, Tai-Min;Kim, Jin-Seong;Lee, Hee-Soo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.22 no.2
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    • pp.78-83
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    • 2012
  • The structural change and the electrical conductivity with Sr content in $La_{1-x}Sr_xMn_{0.8}Cu_{0.2}O_3$ (LSMCu) were studied. $La_{0.8}Sr_{0.2}MnO_3$ (LSM) and $La_{1-x}Sr_xMn_{0.8}Cu_{0.2}O_3$ ($0.1{\leq}x{\leq}0.4$) were synthesized by EDTA citric complexing process (ECCP). A decrease in the lattice parameters and lattice volumes was observed with increase of Sr content, and these results were attributed to the increasing $Mn^{4+}$ ions and $Cu^{3+}$ ions in B-site. The electrical conductivity measured from $500^{\circ}C$ to $1000^{\circ}C$ was increased with increase of Sr content in the $0.1{\leq}x{\leq}0.3$ composition range, and it was 172.6 S/cm (at $750^{\circ}C$) and 177.7 S/cm (at $950^{\circ}C$, the maximum value) in x = 0.3. The electrical conductivity was decreased in x = 0.4 because of the presence of the second phase in the grain boundaries. The lattice volume was contracted by increase of $Mn^{4+}$ ions and $Cu^{3+}$ ions in B-site according to increase of Sr content and the electrical conductivity was increased with increase of charge carriers which were involved in the hopping mechanism.

Electrochemical properties of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$ cathodes for medium-temperature SOFC (중간온도형 고체산화물 연료전지의 양극재료로서 $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$의 전기화학특성)

  • Ryu Ji-H.;Jang Jong-H.;Lee Hee-Y.;Oh Seung-M.
    • Journal of the Korean Electrochemical Society
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    • v.1 no.1
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    • pp.1-7
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    • 1998
  • For the purpose of finding new cathode materials for medium-temperature $(700\~800^{\circ}C)$ solid oxide fuel cells, $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$ are prepared, and their thermal stability and conductivity characteristics are investigated. Also, the cathodic activities are measured after the cathode layer being attached on CGO (cerium-gadolinium oxide) electrolyte disk. The X-ray analyses indicate that the materials prepared by calcining the citrate-gels at $800^{\circ}C$ have the orthorhombic perovskite structure without discernible impurities. The thermal stability of the undoped Co perovskite is so poor that it is decomposed to the individual binary oxide even at $1300^{\circ}C$. But the partially Fe-doped cobaltates exhibit a better thermal stability to retain their structural integrity up to $1400^{\circ}C$. The observation whereby both the undoped and Fe-doped cobaltates melt at ca. $1300^{\circ}C$ leads us to perform the electrode adhesion at <$1300^{\circ}C$. The cathodic activity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$, electrodes is superior to $La_{0.9}Sr_{0.1}MnO_3$, among the samples of $x=0.0\~0.5$, the x=0.2 cathode shows the best activity for the oxygen reduction reaction. It is likely that the Fe-doping provides a better thermal stability to the materials but in turn imparts an inferior cathodic activity, such that the optimum trade-off is made at x=0.2 between the two factors. The total electrical conductivity and ion conductivity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$, are measured to be 51 S/cm and $6.0\times10^{-4}S/cm\;at\;800^{\circ}C$, respectively. The conductivity values illustrate that the materials are a mixed conductor and the reaction sites can be expanded to the overall electrode surface, thereby providing a better cathodic activity than $La_{0.9}Sr_{0.1}MnO_3$.

Effects of an $Al_2$O$_3$Surfasce Protective Layer on the Sensing Properties of $SnO_2$Thin Film Gas Sensors (Al$_2$O$_3$ 표면 보호층이 박막형 $SnO_2$ 가스센서의 감지 특성에 미치는 영향)

  • Seong, Gyeong-Pil;Choe, Dong-Su;Kim, Jin-Hyeok;Mun, Jong-Ha;Myeong, Tae-Ho
    • Korean Journal of Materials Research
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    • v.10 no.11
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    • pp.778-783
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    • 2000
  • Effects of the $Al_2$O$_3$surface protective layer, deposited on the SnO$_2$sensing layer by aerosol flame deposition (AFD) method, on the sensing properties of SnO$_2$thin film ags sensors were investigated.Effects of Pt doping to the $Al_2$O$_3$surface protective layer on the selectivity of CH$_4$ gas were also investigated. 0.3$\mu\textrm{m}$ thick SnO$_2$thin sensing layers on Pt electrodes were prepared by R.F. magnetron sputtering with R.F. power of 50 W, at working pressure of 4mTorr, and at 20$0^{\circ}C$ for 30 min. $Al_2$O$_3$surface protective layers on SnO$_2$layers were prepared by AFD using a diluted aluminum nitrade (Al(NO$_3$).9$H_2O$) solution. The sensitivity of CO gas in the SnO$_2$gas sensor with an $Al_2$O$_3$surface protective layer was significantly decreased. But that of CH$_4$gas remained almost same with pure SnO$_2$gas sensor. This result shows that the selectivity of CH$_4$gas is increased because of the $Al_2$O$_3$surface protective layer. In the case of SnO$_2$gas sensors with Pt-doped $Al_2$O$_3$surface protective layers, low sensing property to CO gas and high sensing property to CH$_4$were observed. This results in the increasing of selectivity of CH$_4$gas selectivity are discussed.

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