• Title/Summary/Keyword: $CH_4$ oxidation

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Mechanism for the Oxidation Reaction of Alcohols Using Cr(VI)-Pyrazine Complex (크롬(VI)-피라진 착물을 이용한 알코올류의 산화반응과 메카니즘)

  • Park, Young Cho;Kim, Young Sik
    • Applied Chemistry for Engineering
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    • v.27 no.1
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    • pp.110-114
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    • 2016
  • Cr(VI)-pyrazine complex (PZCC) was synthesized by the reaction of pyrazine with chromium (VI) trioxide in 6 M HCl. The structure was characterized using IR spectroscopy and inductively coupled plasma (ICP). The oxidation of benzyl alcohol using PZCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: N,N'-dimethylform-amide > acetone > chloroform > cyclohexene. In the presence of N,N'-dimethylformamide solvent with an acidic catalyst such as sulfuric acid ($H_2SO_4$ solution), PZCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate-determining step.

Oxidation Characteristics of Methanol on Pt/C and Pt-Ru/C Catalyst for the Anode of Direct Methanol Fuel Cell (Pt/C 및 Pt-Ru/C 촉매를 사용한 직접 메탄올 연료전지 연료극의 메탄올 산화 반응 특성)

  • 정두환;이창형;신동열
    • Journal of Energy Engineering
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    • v.7 no.1
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    • pp.35-43
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    • 1998
  • Electrodes using for the anode electrode of direct methanol fuel cell with Pt/C and Pt/Ru/C catalyst were prepared and characterized by SEM, TEM, thermal analysis and electrochemical analysis. The half cell tests were carried out with 1 M $H_2SO_4$ electrolyte and 1 M $CH_3OH$ in order to evaluate the electrode performance. The employed electrochemical methods were cyclic vol-tammetry and potentiodynamic polarization experiments. It was found that 20 w% polytetrafluoroethylene (PTFE) content in catalyst showed the best performance due to the best platinum utilization on PTFE-containing catalyst layer. It was found that Pt/Ru/C binary catalyst inhibited the poisoning of anode electrode showing improved performance compared to the Pt/C catalyst by the adsorption of oxygen containing species on the electrode surface at same time. The apparent activation energy for methanol oxidation on the Pt/Ru/C and Pt/C catalyst layer was 11.60 kJ/mol and 26.85 kJ/mol, respectively.

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The effect of initial Pd catalyst oxidation stale on CH$_4$sensitivity of SnO$_2$thin film sensor (Pd 촉매의 부분 산화 조절을 이용한 SnO$_2$박막 센서의 CH$_4$감도 변화 연구)

  • Choi, W. K.;Cho, J.;Cho, J. S.;Song, J. H.;Jung, H. J.;Koh, S. K.
    • Journal of the Microelectronics and Packaging Society
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    • v.6 no.2
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    • pp.45-49
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    • 1999
  • A flammable gas sensor based on the $SnO_2$thin film deposited by the reactive ion assisted deposition was fabricated and ultra-thin Pd layer as catalyst was adsorbed at surface by ion beam sputtering. The initial oxidation states of Pd catalyst were controlled to investigate the role of Pd in the sensing process of inflammale gas sensor through annealing in air and vacuum respectively. The Pd catalyst existing in pure metallic state showed the sensitivity higher than that of PdO. The result might be closely related to the fact that PdO as a surface acceptor would receive electrons via Pd sub-channel from $SnO_2$, and thus which reduces the sensitivity and delay the response time.

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Kinetics of the Oxidation of Substituted Benzyl Alcohols using 6-Methylquinolinium Dichromate (6-Methylquinolinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.12 no.12
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    • pp.5990-5996
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    • 2011
  • 6-Methylquinolinium dichromate[$(C_{10}H_9NH)_2Cr_2O_7$] was synthesized by the reaction of 6-methylquinoline with chromium trioxide in $H_2O$, and characterized by IR, ICP. The oxidation of benzyl alcohol using 6-methylquinolinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene < chloroform < acetone < N,N- dimethylformamide. In the presence of hydrochloric acid($H_2SO_4$ solution), 6-methylquinolinium dichromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.67(303K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

Kinetic Study on the Oxidation Reaction of Substituted Benzyl Alcohols by Cr(VI)-Heterocyclic Complex (2,2'-Bipyridinium Dichromate) (크롬(VI)-헤테로고리 착물(2,2'-Bipyridinium Dichromate)에 의한 치환 벤질 알코올류의 산화반응에 대한 속도론적 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.23 no.2
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    • pp.241-246
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    • 2012
  • Cr(VI)-heterocyclic complex (2,2'-bipyridinium dichromate) was synthesized by the reaction between of 2,2'-bipyridine and chromium trioxide in $H_2O$, and characterized by IR and ICP. The oxidation of benzyl alcohol using 2,2'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexene < chloroform < acetone < N,N-dimethylformamide. In the presence of DMF solvent with acidic catalyst such as $H_2SO_4$ solution, 2,2'-bipyridinium dichromate oxidized the benzyl alcohol and its derivatives (p-$p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant was -0.66 (303 K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

SnO2 Hollow Hemisphere Array for Methane Gas Sensing

  • Hieu, Nguyen Minh;Vuong, Nguyen Minh;Kim, Dojin;Choi, Byung Il;Kim, Myungbae
    • Korean Journal of Materials Research
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    • v.24 no.9
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    • pp.451-457
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    • 2014
  • We developed a high-performance methane gas sensor based on a $SnO_2$ hollow hemisphere array structure of nano-thickness. The sensor structures were fabricated by sputter deposition of Sn metal over an array of polystyrene spheres distributed on a planar substrate, followed by an oxidation process to oxidize the Sn to $SnO_2$ while removing the polystyrene template cores. The surface morphology and structural properties were examined by scanning electron microscopy. An optimization of the structure for methane sensing was also carried out. The effects of oxidation temperature, film thickness, gold doping, and morphology were examined. An impressive response of ~220% was observed for a 200 ppm concentration of $CH_4$ gas at an operating temperature of $400^{\circ}C$ for a sample fabricated by 30 sec sputtering of Sn, and oxidation at $800^{\circ}C$ for 2 hr in air. This high response was enabled by the open structure of the hemisphere array thin films.

Investigation of Oxidation Behavior of Alloy 617 under Air/Helium Environments at 950℃ (니켈기 합금 Alloy 617의 950℃ 대기/헬륨 분위기에서 산화거동 고찰)

  • Jung, Sujin;Lee, Gyeong-Geun;Kim, Dong-Jin
    • Corrosion Science and Technology
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    • v.17 no.5
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    • pp.218-224
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    • 2018
  • Alloy 617 is a candidate Ni-based superalloy for intermediate heat exchanger (IHX) of a high-temperature gas reactor (VHTR), because of its good creep strength and corrosion resistance at high temperature. Small amount of impurities such as $H_2O$, $H_2$, CO and $CH_4$ are introduced inevitably in helium, as a coolant during operation of a VHTR. Reactions of material and impurities are accelerated with increase of temperature to $950^{\circ}C$ of operating temperature of a VHTR, leading to material corrosion aggravation. In this circumstance, high-temperature corrosion tests were performed at $950^{\circ}C$ in air and impure helium environments, up to 250 hours in this study. Oxidation rate of $950^{\circ}C$ in an air environment was higher than that of impure helium, explained by difference in outer oxide morphology and microstructure as a function of oxygen partial pressure. An equiaxed Cr-rich surface oxide layer was formed in an air environment, and a columnar Cr-rich oxide was formed in an impure helium environment.

Methanol oxidation behaviors of PtRu nanoparticles deposited onto binary carbon supports for direct methanol fuel cells

  • Park, Soo-Jin;Park, Jeong-Min;Lee, Seul-Yi
    • Carbon letters
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    • v.14 no.2
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    • pp.121-125
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    • 2013
  • In this study, PtRu nanoparticles deposited on binary carbon supports were developed for use in direct methanol fuel cells using carbon blacks (CBs) and multi-walled carbon nanotubes (MWCNTs). The particle sizes and morphological structures of the catalysts were analyzed using X-ray diffraction and transmission electron microscopy, and the PtRu loading content was determined using an inductively coupled plasma-mass spectrometer. The electrocatalytic characteristics for methanol oxidation were evaluated by means of cyclic voltammetry with 1 M $CH_3OH$ in a 0.5 M $H_2SO_4$ solution as the electrolyte. The PtRu particle sizes and the loading level were found to be dependent on the mixing ratio of the two carbon materials. The electroactivity of the catalysts increased with an increasing MWCNT content, reaching a maximum at 30% MWCNTs, and subsequently decreased. This was attributed to the introduction of MWCNTs as a secondary support, which provided a highly accessible surface area and caused morphological changes in the carbon supports. Consequently, the PtRu nanoparticles deposited on the binary support exhibited better performance than those deposited on the single support, and the best performance was obtained when the mass ratio of CBs to MWCNTs was 70:30.

Continuous Operation of $CO_2$/NOx-free 50kW Checmial-Looping Combustor ($CO_2$/NOx-free 50kW 매체순환식 가스연소기 산화-환원 연속반응 실증)

  • Ryu, Ho-Jung;Jin, Gyoung-Tae;Yi, Chang-Keun
    • 한국연소학회:학술대회논문집
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    • 2004.06a
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    • pp.227-234
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    • 2004
  • For gaseous fuel combustion with inherent $CO_2$ capture and low NOx emission, chemical-looping combustion(CLC) may yield great advantages of savings of energy to $CO_2$ separation and suppressing the effect on environment. In chemical-looping combustor, fuel is oxidized by metal oxide medium (oxygen carrier particle) in a reduction reactor. Reduced particles are transported to oxidation reactor and oxidized by air and recycled to reduction reactor. The fuel and the air are never mixed, and the gases from reduction reactor, $CO_2$ and $H_2O$, leave the system as separate stream. The $H_2O$ can be easily separated by condensation and pure $CO_2$ is obtained without any loss of energy for separation. The purpose of this study is to demonstrate inherent $CO_2$ separation and no NOx emission and to confirm high $CO_2$ selectivity, no side reaction (i.e., carbon deposition, hydrogen generation) by continuous reduction and oxidation experiment in a 50kWtb chemical-looping combustor. NiO/bentonite particle was used as a bed material and $CH_4$ and air were used as reacting gases for reduction and oxidation respectively.

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Synthesis, Characterization and Liquid Phase Oxidation of Cyclohexane with Hydrogen Peroxide over Oxovanadium(IV) Schiff-base Tetradendate Complex Covalently Anchored to Multi-Wall Carbon Nanotubes (MWNTs)

  • Salavati-Niasari, Masoud;Bazarganipour, Mehdi
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.355-362
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    • 2009
  • The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized oxovanadium(IV) Schiff-base; N,N'-bis(4-hydroxysalicylidene)-ethylene-1, 2-diamineoxovanadium(IV), [VO($(OH)_2$-salen)]; has been covalently anchored on modified MWNTs. The new modified MWNTs ([VO($(OH)_2$-salen)]-MWNTs]) have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), UV-Vis, Diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The analytical data indicated a composition corresponding to the mononuclear complex of tetradentate Schiff-base ligand. The characterization of the data showed the absence of extraneous complex, retention of MWNTs and covalently anchored on modified MWNTs. Liquid-phase oxidation of cyclohexane with $H_2O_2$ to a mixture of cyclohexanone, cyclohexanol and cyclohexane-1,2-diol in $CH_3$CN have been reported using oxovanadium(IV) Schiff-base complex covalently anchored on modified MWNTs as catalysts. This catalyst is more selective toward cyclohexanol formation.