• Title/Summary/Keyword: Strong metal to support interaction

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Revealing Strong Metal Support Interaction during CO Oxidation with Metal Nanoparticle on Reducible Oxide Substrates

  • Park, Dahee;Kim, Sun Mi;Qadir, Kamran;Park, Jeong Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.264-264
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    • 2013
  • Strong metal-support interaction effect is an important issue in determining the catalytic ac-tivity for heterogeneous catalysis. In this study, we investigated the support effect and the role of organic capping layers of two-dimensional Pt nanocatalysts on reducible metal oxide supports under the CO oxidation. Several reducible metal oxide supports including CeO2, Nb2O5, and TiO2 thin films were prepared via sol-gel techniques. The structure, chemical state and optical property were characterized using XRD, XPS, TEM, SEM, and UV-VIS spectrometer. We found that the reducible metal oxide supports have a homogeneous thin thickness and crystalline structure after annealing at high temperature showing the different optical band gap energy. Langmuir-Blodgett technique and arc plasma deposition process were employed to ob-tain Pt nanoparticle arrays with capping and without capping layers, respectively on the oxide support to assess the role of the supports and capping layers on the catalytic activity of Pt catalysts under the CO oxidation. The catalytic performance of CO oxidation over Pt supported on metal oxide thin films under oxidizing reaction conditions (40 Torr CO and 100 Torr O2) was tested. The results show that the catalytic activity significantly depends on the metal oxide support and organic capping layers of Pt nanoparticles, revealing the strong metal-support interaction on these nanocatalysts systems.

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Enhancement of coke resistance on Ni/MgO-$Al_2O_3$ catalyst in combined $H_2O$ and $CO_2$ reforming of $CH_4$ for the syngas production (합성가스 생산을 위한 복합개질 반응에서 $Ni/MgO-Al_2O_3$ 촉매의 탄소 침적 저항성 향상에 관한 연구)

  • Koo, Kee-Young;Roh, Hyun-Seog;Jung, Un-Ho;Yoon, Wang-Lai
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.06a
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    • pp.727-730
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    • 2009
  • Highly active and stable nano-sized Ni catalysts supported on MgO-$Al_2O_3$ calcined from hydrotalcite-like materials have been successfully developed with a strong metal to support interaction (SMSI) to enhance the coke resistance in combined $H_2O$ and $CO_2$ reforming of $CH_4$ (CSCRM) for syngas ($H_2$/CO=2) production. The change of the surface area and NiO crystallite size with varying the pre-calcination temperature of support and Mgo content was investigated in relation to the coke resistance. As increasing the pre-calcination temperature, the surface area decreases and the metal to support interaction becomes weak. As a consequence, the coke deposition was more severe on catalysts pre-calcined at high temperature. It was concluded that highly dispersed Ni metal in the surface of Ni/MgO-$Al_2O_3$ catalyst (MgO=30 wt%) pre-calcined at $800^{\circ}C$ had a strong metal to support interaction (SMSI) resulting in an increase of coke resistance and high activity.

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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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Support Effect of Arc Plasma Deposited Pt Nanoparticles/TiO2 Substrate on Catalytic Activity of CO Oxidation

  • Qadir, Kamran;Kim, Sang Hoon;Kim, Sun Mi;Ha, Heonphil;Park, Jeong Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.261-261
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    • 2013
  • The smart design of nanocatalysts can improve the catalytic activity of transition metals on reducible oxide supports, such as titania, via strong metal-support interactions. In this work, we investigatedtwo-dimensional Pt nanoparticle/titania catalytic systems under the CO oxidation reaction. Arc plasma deposition (APD) and metal impregnation techniques were employed to achieve Pt nanoparticle deposition on titania supports, which were prepared by multitarget sputtering and sol-gel techniques. APD Pt nanoparticles with an average size of 2.7 nm were deposited on sputtered and sol-gel-prepared titania films to assess the role of the titania support on the catalytic activity of Pt under CO oxidation. In order to study the nature of the dispersed metallic phase and its effect on the activity of the catalytic CO oxidation reaction, Pt nanoparticles were deposited in varying surface coverages on sputtered titania films using arc plasma deposition. Our results show an enhanced activity of Pt nanoparticles when the nanoparticle/titania interfaces are exposed. APD Pt shows superior catalytic activity under CO oxidation, as compared to impregnated Pt nanoparticles, due to the catalytically active nature of the mild surface oxidation and the active Pt metal, suggesting that APD can be used for large-scale synthesis of active metal nanocatalysts.

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Heavy Metal Interactions during Accumulation and Elimination of Cadmium and Copper in the Liver of Juvenile Flounder, Paralichthys olivaceus

  • Kim Seong-Gil;Kim Sang-Gyu;Kang Ju-Chan
    • Fisheries and Aquatic Sciences
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    • v.5 no.4
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    • pp.295-301
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    • 2002
  • Experiments were carried out to investigate the effects of metal interaction on the accumulation and elimination of Cd and Cu in the liver of flounder, Paralichthys olivaceus, exposed to sub-chronic Cd (0, 5, 10, 50, 100 ${\mu}g/L$)/Cu $(10 {\mu}g/L)$ mixture. Cd exposure resulted in an increased Cd accumulation in the liver of flounder for exposure periods and concentration, and Cd accumulation increased linearly with exposure time. Cu accumulation profiles were similar to those of Cd. Cd concentration in the liver significantly decreased at the 10th depuration period and elimination rate was $66.20\%,\;86.22\%$ in 50 and $100 {\mu}g/L$at the end of depuration periods, respectively. Although, Cu elimination was similar to Cd elimination phase, Cd elimination rate was higher than that of Cu. Co-relationship of Cd and Cu have a positive correlation coefficient r=0.8620 (P<0.001) and support the strong relationship between Cd and Cu accumulation. As increase with the Cd exposure concentration, there were significant (P<0.001) differences between Cd and Cu accumulation.

Fabrication of carbon nanotube emitters by filtration through a metal mesh

  • Choi, Ju-Sung;Lee, Han-Sung;Gwak, Jeung-Chun;Lee, Nae-Sung
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2010.06a
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    • pp.150-150
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    • 2010
  • Carbon nanotubes have drawn attention as one of the most promising emitter materials ever known not only due to their nanometer-scale radius of curvature at tip and extremely high aspect ratios but also due to their strong mechanical strength, excellent thermal conductivity, good chemical stability, etc. Some applications of CNTs as emitters, such as X-ray tubes and microwave amplifiers, require high current emission over a small emitter area. The field emission for high current density often damages CNT emitters by Joule heating, field evaporation, or electrostatic interaction. In order to endure the high current density emission, CNT emitters should be optimally fabricated in terms of material properties and morphological aspects: highly crystalline CNT materials, low gas emission during electron emission in vacuum, optimal emitter distribution density, optimal aspect ratio of emitters, uniform emitter height, strong emitter adhesion onto a substrate, etc. We attempted a novel approach to fabricate CNT emitters to meet some of requirements described above, including highly crystalline CNT materials, low gas emission, and strong emitter adhesion. In this study, CNT emitters were fabricated by filtrating an aqueous suspension of highly crystalline thin multiwalled CNTs (Hanwha Nanotech Inc.) through a metal mesh. The metal mesh served as a support and fixture frame of CNT emitters. When 5 ml of the CNT suspension was engaged in filtration through a 400 mesh, the CNT layers were formed to be as thick as the mesh at the mesh openings. The CNT emitter sample of $1{\times}1\;cm^2$ in size was characteristic of the turn-on electrical field of 2.7 V/${\mu}m$ and the current density of 14.5 mA at 5.8 V/${\mu}m$ without noticeable deterioration of emitters. This study seems to provide a novel fabrication route to simply produce small-size CNT emitters for high current emission with reliability.

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Effect of La in Partial Oxidation of Methane to Hydrogen over M(1)-Ni(5)/AlCeO3 (M = La, Ce, Y) Catalysts (M(1)-Ni(5)/AlCeO3 (M = La, Ce, Y) 촉매상에서 수소 제조를 위한 메탄의 부분산화반응에서 La의 효과)

  • Seo, Ho Joon
    • Applied Chemistry for Engineering
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    • v.30 no.6
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    • pp.757-761
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    • 2019
  • The catalytic yields of POM to hydrogen over M(1)-Ni(5)/AlCeO3 (M = La, Ce, Y) were investigated using a fixed bed flow reactor under atmosphere. The crystal phase behavior of reduced La(1)-Ni(5)/AlCeO3 catalysts before and after the reaction were studied via XRD analysis. FESEM and EDS analyses were further performed to show the uniformed distribution of La, Ni, and Ce metal particles on the catalyst surface. XPS results showed O2-, O22- species and metal ions such as Ce3+, Ce4+, La3+ and Ni2+ etc. were on the catalyst surface. When 1 wt% of La was added to Ni(5)/AlCeO3 catalyst, Ni2p3/2 and Ce3d5/2 increased 52.7 and 6.3%, respectively. The yield of hydrogen on the La(1)-Ni(5)/AlCeO3 catalyst was 89.1%, which was much better than that of M(1)-Ni(5)/AlCeO3 (M = Ce, Y). As Ce4+ ions of CeO2 produced by the reaction of AlCeO3 with oxygen were substitute to La3+, it made oxygen vacancies in the lattice and further improved the hydrogen yield by increasing the dispersion of Ni atoms with strong metal-support interaction (SMSI) effect.

The Effect of Calcination Temperature on the Performance of Ni-Ce0.8Zr0.2O2 Catalysts for Steam Reforming of Methane under Severe Conditions (가혹한 조건의 SRM 반응에서 Ni-Ce0.8Zr0.2O2 촉매의 소성온도에 따른 영향)

  • Jang, Won-Jun;Jeong, Dae-Woon;Shim, Jae-Oh;Roh, Hyun-Seog
    • Transactions of the Korean hydrogen and new energy society
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    • v.23 no.3
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    • pp.213-218
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    • 2012
  • Steam reforming of methane (SRM) is the primary method to produce hydrogen. Commercial Ni-based catalysts have been optimized for SRM with excess steam ($H_2O/CH_4$ > 2.5) at high temperatures (> $700^{\circ}C$). However, commercial catalysts are not suitable under severe conditions such as stoichiometric steam over methane ratio ($H_2O/CH_4$ = 1.0) and low temperature ($600^{\circ}C$). In this study, 15wt.% Ni catalysts supported on $Ce_{0.8}Zr_{0.2}O_2$ were prepared at various calcination temperatures for SRM at a very high gas hourly space velocity (GHSV) of $621,704h^{-1}$. The calcination temperature was systematically varied to optimize 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst at a $H_2O/CH_4$ ratio of 1.0 and at $600^{\circ}C$. 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ exhibited the highest $CH_4$ conversion as well as stability with time on stream. Also, 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ showed the highest $H_2$ yield (58%) and CO yield (21%) among the catalysts. This is due to complex NiO species, which have relatively strong metal to support interaction (SMSI).

Effect of Eu in Partial Oxidation of Methane to Hydrogen over Ln(1)-Ni(5)/SBA-15 (Ln = Dy, Eu, Pr, and Tb) Catalysts (Ln(1)-Ni(5)/SBA-15 (Ln = Dy, Eu, Pr, Tb) 촉매상에서 수소제조를 위한 메탄의 부분 산화 반응에서 Eu의 효과)

  • Seo, Ho Joon
    • Applied Chemistry for Engineering
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    • v.32 no.4
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    • pp.478-482
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    • 2021
  • The catalytic yields of partial oxidation of methane (POM) to hydrogen over Ln(1)-Ni(5)/SBA-15 (Ln = Dy, Eu, Pr, and Tb) were investigated in a fixed bed flow reactor under atmosphere. As 1 wt% of Eu was added to Ni(5)/SBA-15 catalyst, the O1s and Si2p core electron levels of Eu(1)-Ni(5)/SBA-15 showed the chemical shift by XPS. XPS analysis also demonstrated that the atomic ratio of O1s, Ni2p3/2, and Si2p increased to 1.284, 1.298, and 1.058, respectively, and exhibited O-, and O2- oxygen and metal ions such as Eu3+, Ni0, Ni2+, and Si4+ on the catalyst surface. The yield of hydrogen on the Eu(1)-Ni(5)/SBA-15 was 57.2%, which was better than that of Ln(1)-Ni(5)/SBA-15 (Ln = Dy, Pr, and Tb), the catalytic activity was kept steady even 25 h. As 1 wt% of Eu was added to Ni(5)/SBA-15, the oxygen vacancies caused by strong metal-support interaction (SMSI) effect due to the strong interaction between metals and carrier are made. They are resulted in increasing the dispersion of Ni0, and Ni2+ nano particles on the surface of catalyst, and are kept catalytic activity.

Synthesis of Ethylamines for the Reductive Amination of Ethanol over Ni Catalysts: Effect of Supports (니켈 촉매상에서 에탄올의 환원성 아민화반응에 의한 에틸아민 제조 : 담체의 영향)

  • Jeong, Ye-Seul;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.57 no.5
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    • pp.714-722
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    • 2019
  • Catalysts were prepared by using incipient wetness impregnation method with 17 wt% Ni on a support ($SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, $SiO_2$, $TiO_2$, MgO) and the catalytic activity in the reductive amination of ethanol with ammonia in the presence of hydrogen was compared and evaluated. The catalysts used before and after the reaction were characterized using X-ray diffraction, nitrogen adsorption, ethanol-temperature programmed desorption (EtOH-TPD), isopropanol-temperature programmed desorption (IPA-TPD), and hydrogen chemisorption etc. In the case of preparing $ZrO_2$ and $Y_2O_3$ supports, the small amount of Si dissolution from the Pyrex reactor surface provoked the formation of mixed oxides $SiO_2-ZrO_2$ and $SiO_2-Y_2O_3$. Among the catalysts used, $Ni/SiO_2-Y_2O_3$ catalyst showed the best activity, and this good activity was closely related to the highest nickel dispersion, and low desorption temperature in EtOH-TPD and IPA-TPD. The low catalytic activity on Ni/MgO catalysts showed low activity due to the formation of NiO-MgO solid-solutions. In the case of $Ni/TiO_2$, the reactivity was low due to the low nickel metal phase due to strong metal-support interaction. In the case of using a support as $SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, and $SiO_2$, the selectivities of ethylamines and acetonitrile were not significantly different at similar ethanol conversion.