• Title/Summary/Keyword: catalytic reactivity

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$TiO_2$-Ni inverse Catalyst for CRM Reactions with High Resistance to Coke Formation

  • Seo, Hyun-Ook;Sim, Jong-Ki;Kim, Kwang-Dae;Kim, Young-Dok;Lim, Dong-Chan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.267-267
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    • 2012
  • $TiO_2$-Ni inverse catalysts were prepared using atomic layer deposition (ALD) process and catalytic $CO_2$ reforming of methane (CRM) reaction over catalysts (either bare Ni or $TiO_2$ coated-Ni particles) were performed using a continuous flow reactor at $800^{\circ}C$. $TiO_2$-Ni inverse catalyst showed higher catalytic reactivity at initial stage of CRM reactions at $800^{\circ}C$ comparing to bare Ni catalysts. Moreover, catalytic activity of $TiO_2$/Ni catalyst was kept high during 13 hrs of the CRM reactions at $800^{\circ}C$, whereas deactivation of bare Ni surface was started within 1hr under same conditions. The results of surface analysis using SEM, XPS, and Raman showed that deposition of graphitic carbon was effectively suppressed in a presence of $TiO_2$ nanoparticles on Ni surface, thereby improving catalytic reactivity and stability of $TiO_2$/Ni catalytic systems. We suggest that utilizing decoration effect of metal catalyst with oxide nanoaprticles is of great potential to develop metal-based catalysts with high stability and reactivity.

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Catalytic Reactivity of Transition Metal (Pd, Ni) complexes with Aminophosphines; I. Carbon-Carbon coupling reactions (Aminophosphine류가 배위된 전이금속(Pd, Ni) 착물의 촉매반응; I. 탄소-탄소 짝지움 반응)

  • Jung, Maeng-Joon;Lee, Chul-Jae;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.7 no.1
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    • pp.107-113
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    • 2004
  • Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

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Catalytic NiO Filter Supported on Carbon Fiber for Oxidation of Volatile Organic Compounds

  • Sim, Jong Ki;Seo, Hyun Ook;Jeong, Myung-Geun;Kim, Kwang-Dae;Kim, Young Dok;Lim, Dong Chan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2105-2110
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    • 2013
  • Carbon-fiber-supported NiO catalytic filters for oxidation of volatile organic compounds were prepared by electroless Ni-P plating and subsequent annealing processes. Surface structure and crystallinity of NiO film on carbon fiber could be modified by post-annealing at different temperatures (500 and $650^{\circ}C$). Catalytic thermal decompositions of toluene over these catalytic filters were investigated. $500^{\circ}C$-annealed sample showed a higher catalytic reactivity toward toluene decomposition than $650^{\circ}C$-annealed one under same conditions, despite of its lower surface area and toluene adsorption capacity. X-ray diffraction and X-ray photoelectron spectroscopy studies suggest that amorphous structures of NiO on $500^{\circ}C$-annealed catalyst caused the higher reactivity for oxidation of toluene than that of $650^{\circ}C$-annealed sample with a higher crystallinity.

Catalytic Oxidation of Toluene Using NiO Filter Supported on Carbon Fiber

  • Sim, Jong Ki;Seo, Hyun Ook;Jeong, Myung-Geun;Kim, Kwang-Dae;Nam, Jong Won;Kim, Young Dok;Lim, Dong Chan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.217-217
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    • 2013
  • Carbon-fiber-supported NiO catalytic filters for oxidation of volatile organic compounds were prepared by electroless Ni-P plating and subsequent annealing processes. Surface structure and crystallinity of NiO film on carbon fiber could be modified by post-annealing at different temperatures (500 and $650^{\circ}C$. Catalytic thermal decompositions of toluene over these catalytic filters were investigated. $500^{\circ}C$ annealed sample showed a higher catalytic reactivity toward toluene decomposition than $650^{\circ}C$ annealed one under same conditions, despite of its lower surface area and toluene adsorption capacity. X-ray diffraction and X-ray photoelectron spectroscopy studies suggested that amorphous structures of NiO on $500^{\circ}C$ annealed catalyst caused the higher reactivity for oxidation of toluene than that of $650^{\circ}C$ annealed sample with a higher crystallinity.

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Photoemission study on the reactivity of organic molecules on chemically modified TiO2(001) surfaces

  • Gong, Ja-Hyeon;Park, Sang-Min;Hwang, Han-Na;Hwang, Chan-Guk;Kim, Yu-Gwon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.87-87
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    • 2010
  • Adsorption and subsequent catalytic reactions of ethanol and acetaldehyde on chemically modified rutile TiO2(001) surfaces are probed by x-ray photoemission spectroscopy (XPS) using synchrotron radiation. TiO2 is a well-known photocatalyst for various catalytic reactions including oxidation of organic molecules. In this respect, the surface atomic structure has been found to play a vital role in determining the catalytic reactivity and selectivity of TiO2. In this study, we employ an atomically well-ordered reduced TiO2(001) surface which is prepared in a UHV chamber by repeated Ar+-sputtering and annealing (900 K) cycles. We systematically modify the surface by treating the surface with H2O or O2 at room temperature (RT). The catalytic reactivity of the surface-modified TiO2(001) is evaluated by dosing ethanol/acetaldehyde onto the surface at RT and by subsequent annealing to higher temperatures (400~600 K). XPS spectra of C 1s core level are intensively used to probe any change in the oxidation state of carbon atoms. We find that the reactivity as well as the saturation coverage are significantly affected by the RT-treatment of the TiO2 surface with H2O or O2. For both reactant molecules (ethanol/acetaldehyde), oxidation reactions are found to be enhanced on the O2-treated surface compared with the reduced or H2O-treated surfaces. Possibly reaction pathways are discussed based on the observed XPS spectra.

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Influence of VOCs Structure on Catalytic Oxidation Kinetics (휘발성 유기화합물(VOCs)의 촉매산화 전환에서 결합구조의 영향 및 속도특성)

  • 이승범;윤용수;홍인권;이재동
    • Journal of environmental and Sanitary engineering
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    • v.15 no.4
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    • pp.44-51
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    • 2000
  • The reactivity of a range of volatile organic compounds with differing functional groups observed over 0.5% $Pt/{\gamma}-Al_2O_3$ catalyst. In general, the reactivity pattern observed was alcohols > aromatics > ketones > cycloalkane > alkanes. The deep conversion was increased as reaction temperature was increased. A correlation was found between the reactivity of the individual and the strength of the weakest C-Hbond in structure. The conversion of volatile organic compounds increases in order methanol > benzene > cyclohexane > MEK > n-hexane. That is the effect of differences in total dissociation energy. An apparent zeroth-order kinetics with respect to inlet concentration have been observed. A simple multicomponent model based on two-stage redox model made reasonably good predictions of conversion over the range of parameters studied. thus, the catalytic process was suggested as the new VOCs control technology.

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Investigation on Catalytic Combustion of Hydrogen-Air Premixed Gas in 10mm Scale Catalytic Combustor (10mm 스케일 촉매 연소기에서의 수소-공기 예혼합 가스의 연소 현상 관찰)

  • Choi, Won-Young;Kwon, Se-Jin
    • 한국연소학회:학술대회논문집
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    • 2004.11a
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    • pp.181-186
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    • 2004
  • Catalytic combustion is one of the suitable methods which is applicable to micro heat source due to high energy density and no flame quenching. And hydrogen can be oxidized at room temperature with platinum catalyst. So hydrogen-fueled micro catalytic combustor with platinum catalyst can be good and easy-handling heat source for another micro devices. In this work we focused on general catalytic combustion characteristics of hydrogen-air premixed gas in 10mm scale catalytic combustor for the further application to micro scale. Platinum was coated on dense ceramic monolith which can be installed in simple-structured catalytic combustor. We investigated the effect of flow rate, heat loss and platinum percentage in catalyst-coated monolith on catalytic combustion performance by temperature distribution in the combustor. By those results we confirmed catalytic reactivity and estimated reaction area. And we simulated micro scale catalytic reaction by sliced monolith. The results of this work will be important design factors for micro scale catalytic combustor.

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CO Oxidation of Catalytic Filters Consisting of Ni Nanoparticles on Carbon Fiber

  • Seo, Hyun-Ook;Nam, Jong-Won;Kim, Kwang-Dae;Kim, Young-Dok;Lim, Dong-Chan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1199-1203
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    • 2012
  • Catalytic filters consisting of Ni nanoparticle and carbon fiber with different oxidation states of Ni (either metallic or oxidic) were prepared using a chemical vapor deposition process and various post-annealing steps. CO oxidation reactivity of each sample was evaluated using a batch type quartz reactor with a gas mixture of CO (500 mtorr) and $O_2$ (3 torr) at $300^{\circ}C$. Metallic and oxidic Ni showed almost the same CO oxidation reactivity. Moreover, the CO oxidation reactivity of metallic sample remained unchanged in the subsequently performed second reaction experiment. We suggested that metallic Ni transformed into oxidic state at the initial stage of the exposure to the reactant gas mixture, and Ni-oxide was catalytically active species. In addition, we found that CO oxidation reactivity of Ni-oxide surface was enhanced by increase in the $H_2O$ impurity in the reactor.

Photocatalytic Reactivity of Titanium Dioxide in the Removal of Benzene from Air (공기중의 벤젠제거에 대한 산화티타늄 광촉매 반응특성)

  • 박달근
    • Journal of Korean Society for Atmospheric Environment
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    • v.16 no.4
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    • pp.389-398
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    • 2000
  • Photocatalytic removal of benzene from air was examined using titanium dioxide photocatalyst films prepared on soda lime glass(50$\times$50$\times$2 mm) by spin coating and chemical vapor deposition. For the measurement of photocatalytic reactivity titanium dioxide coated glass was placed into a batch reactor and concentration of benzene in the reactor was set to abuot 100 ppm, and then illuminated with UV. It was found that catalytic reactivity of titanium dioxide films increased with the increase of titanium dioxide film thickness and then level off beyond a certain film thickness. UV absorption by the films showed the similar trend. The formation of stoichiometric amount of carbon dioxide was confirmed by measurement of carbon dioxide concentration in the reactor. In general spin coated films revealed better photocatalytic reactivity than chemically deposited one within the experimental ranges covered in this study. Morphology and crystal structure of prepared films were investigated by XRD and SEM and they showed significant difference between spin coated films and CVD films. Highest quantum efficiency of prepared titanium dioxide photocatalyst was close to 50%.

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The Effect of the Changing of C-O-C to C-S-C and C=O to C=S on Reactivity of 4-Nitrophenyl Benzoate with Alkali Metal Ethoxides in Ethanol

  • Kwon, Dong-Sook;Park, Hee-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.93-97
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    • 1991
  • Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides with 4-nitrophenyl benzoate, S-4-nitrophenyl thiobenzoate and 4-nitrophenyl thionbenzoate in ethanol at 25$^{\circ}$C. Substitution of S for O in the leaving group has not affected reactivity significantly, while the effect of the similar replacement in the acyl group has led to rate decrease by a factor of 10, although pronounced rate enhancements have been expected for both systems. The replacement of O by a polarizable S has also influenced the reactivity of the esters toward alkali metal ethoxides, i.e. the reactivity decreases as the size of the metal ion decreases. The alkali metal ions have showed inhibition effect instead of catalytic effect which would have been expected for the present system. The effect of replaced sulfur atom on the reactivity for the present system is attributed to the nature of hard and soft acids and bases.