• Title/Summary/Keyword: chemical oxidation

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Application of Bayer-Villiger Reaction to the Synthesis of Dibenzo-18-crown-6, Dibenzo-21-crown-7 and Dihydroxydibenzo-18-crown-6

  • Utekar, Druman R.;Saman, Shriniwas D.
    • Journal of the Korean Chemical Society
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    • v.58 no.2
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    • pp.193-197
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    • 2014
  • Dibenzo-18-crown-6, dibenzo-21-crown-7 and dihydroxy dibenzo-18-crown-6 were synthesized by Bayer-Villiger oxidation strategy. Dibenzo-18-crown-6 and dibenzo-21-crown-7 could be synthesized through a three-step protocol starting from salicylaldehyde. Salicylaldehyde was reacted with bis-(2-chloroethyl)ether using $K_2CO_3$ in acetonitrile to link the two phenolic groups with the oxyethylene bridge followed by conversion of the formyl group to the hydroxy group via a Baeyer-Villiger reaction and finally linking the two phenolic group with appropriate oxyethylene bridge. The two target crown ethers were obtained in overall yield, 24% and 30%, respectively. This method has a great potential for synthesis of symmetrical as well as unsymmetrical dibenzo crowns with varying oxyethylene bridges. Baeyer-Villiger oxidation could be used to prepare dihydroxy derivative of dibenzo-18-crown-6 through acetylation of dibenzo-18-crown-6 followed by Baeyer-Villiger oxidation. The Baeyer-Villiger oxidation could be substantially accelerated using trifluoroacetic acid.

Combination of ultrasonic assisted liquid phase exfoliation process and oxidation-deoxidation method to prepare large-sized graphene

  • Qi, Lei;Guo, Ruibin;Mo, Zunli;Wu, Qijun
    • Carbon letters
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    • v.25
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    • pp.50-54
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    • 2018
  • Large-size graphene samples are successfully prepared by combining ultrosonic assisted liquid phase exfoliation process with oxidation-deoxidation method. Different from previous works, we used an ultrasound-treated expanded graphite as the raw material and prepared the graphene via a facile oxidation-reduction reaction. Results of X-ray diffraction and Raman spectroscopy confirm the crystal structure of the as-prepared graphene. Scanning electron microscopy images show that this kind of graphene has a large size (with a diameter over $100{\mu}m$), larger than the graphene from graphite powder and flake graphite prepared through single oxidation-deoxidation method. Transmission electron microscopy results also reveal the thin layers of the prepared graphene (number of layers ${\leq}3$). Furthermore, the importance of preprocessing the raw materials is also proven. Therefore, this method is an attractive way for preparing graphene with large size.

Selective Oxidation of Hydrogen Sulfide to Elemental Sulfur with Fe/MgO Catalysts in a Slurry Reactor

  • Lee, Eun-Ku;Jung, Kwang-Deog;Joo, Oh-Shim;Shul, Yong-Gun
    • Bulletin of the Korean Chemical Society
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    • v.26 no.2
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    • pp.281-284
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    • 2005
  • The Fe/MgO catalysts with different Fe loadings (1, 4, 6, 15 and 30 wt% Fe) were prepared by a wet impregnation with iron nitrate as precursor. All of the catalysts were characterized by BET surface analyzer, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). The maximum removal capacity of $H_2S$ was obtained with 15 wt% Fe/MgO catalyst which had the highest BET surface area among the measured catalysts. XRD of Fe/MgO catalysts showed that well dispersed Fe particles could be present on Fe/MgO with Fe loadings below 15 wt%. The crystallites of bulk $\alpha$-$Fe_2O_3$ became evident on 30 wt% Fe/MgO, which were confirmed by XRD. TPR profiles showed that the reducibility of Fe/MgO was strongly related to the loaded amounts of Fe on MgO support. Therefore, the highest removal efficiency of $H_2S$ in wet oxidation could be ascribed to a good dispersion and high reducibility of Fe/MgO catalyst. XPS studies indicated that the $H_2S$ oxidation with Fe/MgO could proceed via the redox mechanism ($Fe^{3+}\;{\leftrightarrow}\;Fe^{2+}$).

Characteristics of Solid Fuel Oxidation in a Molten Carbonate Fuel Cell

  • Lee, Choong-Gon;Kim, Yu-Jeong;Kim, Tae-Kyun;Lee, Sang-Woo
    • Journal of Electrochemical Science and Technology
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    • v.7 no.2
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    • pp.91-96
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    • 2016
  • Oxidation behaviours of ash free coal (AFC), carbon, and H2 fuels were investigated with a coin type molten carbonate fuel cell. Because AFC has no electrical conductivity, its oxidation occurs via gasification to H2 and CO. An interesting behaviour of mass transfer resistance reduction at higher current density was observed. Since the anode reaction has the positive reaction order of H2, CO2 and H2O, the lack of CO2 and H2O from AFC results in a significant mass transfer resistance. However, the anode products of CO2 and H2O at higher current densities raise their partial pressure and mitigate the resistance. The addition of CO2 to AFC reduced the resistance sufficiently, thus the resistance reduction at higher current densities did not appear. Electrochemical impedance results also indicate that the addition of CO2 reduces mass transfer resistance. Carbon and H2 fuels without CO2 and H2O also show similar behaviour to AFC: mass transfer resistance is diminished by raising current density and adding CO2.

Al2O3/SiO2/Si(100) interface properties using wet chemical oxidation for solar cell applications

  • Min, Kwan Hong;Shin, Kyoung Cheol;Kang, Min Gu;Lee, Jeong In;Kim, Donghwan;Song, Hee-eun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.418.2-418.2
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    • 2016
  • $Al_2O_3$ passivation layer has excellent passivation properties at p-type Si surface. This $Al_2O_3$ layer forms thin $SiO_2$ layer at the interface. There were some studies about inserting thermal oxidation process to replace naturally grown oxide during $Al_2O_3$ deposition. They showed improving passivation properties. However, thermal oxidation process has disadvantage of expensive equipment and difficult control of thin layer formation. Wet chemical oxidation has advantages of low cost and easy thin oxide formation. In this study, $Al_2O_3$/$SiO_2/Si(100)$ interface was formed by wet chemical oxidation and PA-ALD process. $SiO_2$ layer at Si wafer was formed by $HCl/H_2O_2$, $H_2SO_4/H_2O_2$ and $HNO_3$, respectively. 20nm $Al_2O_3$ layer on $SiO_2/Si$ was deposited by PA-ALD. This $Al_2O_3/SiO_2/Si(100)$ interface were characterized by capacitance-voltage characteristics and quasi-steady-state photoconductance decay method.

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New Application of Clay Filler for Carbon/Carbon Composites and Improvement of Filler Effect by Clay Size Reduction

  • Jeong, Eui-Gyung;Kim, Jin-Hoon;Lee, Young-Seak
    • Carbon letters
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    • v.11 no.4
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    • pp.293-297
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    • 2010
  • To investigate new potential application of a clay material for C/C composites, illite added C/C composites were prepared with various illite contents. The improvement of filler effect by illite size reduction was also investigated using wet ballmilling by evaluating illite/phenolic resin infiltration using bulk density and porosity measurements, chemical structural changes of the composites using XRD, and thermal oxidation stability in air of the composites using TGA. The size reduction of illite resulted in narrower particle size distribution and improved illite infiltration into carbon preform. And the resultant C/C composites prepared with illite had even more improved thermal oxidation stability in air, showing more increased IDTs up to $100^{\circ}C$, compared to those of the C/C composites with pristine illite, due to the SiC formation through carbothermal reduction between illite and carbon materials. The illite induced delay in oxidation of the illite-C/C composites was also observed and the delayed oxidation behavior was attributed to the layered structure of illite, which improved illite/phenol resin infiltration. Therefore, the potential use of illite as filler to improve oxidation stability of C/C composite can be promising. And the size reduction of illite can improve its effect on the desired properties of illite-C/C composites even more.

Preferential Oxidation of CO over Cu/Ti-SBA-15 Catalysts (Cu 담지 Ti-SBA-15 촉매의 선택적 CO 산화 반응)

  • Kim, Joon-Woo;Park, Jae-Woo;Lee, Jong-Soo;Choi, Han-Seul;Choung, Suk-Jin
    • Korean Chemical Engineering Research
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    • v.51 no.4
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    • pp.432-437
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    • 2013
  • The CO preferential oxidation reaction (PROX) has been done using Cu catalytic active species supported on some of mesoporous silica materials which can facilitate the diffusion of the reactants in order to prevent the poisoning of anode active materials by CO molecules during driving polymer electrolyte fuel cells (PEMFC) in this study. As a result when SBA-15 with large pore used as a support showed excellent CO oxidation activity, especially the activity increased in proportion to the amount of supported Cu. Ti components which was inserted to increase the degree of dispersion of Cu, contributed to improving the performance for CO oxidation at low-temperature. The degree of dispersion of Cu ingredients was the best in the catalyst inserted 20 mol-% Ti into the framework of SBA-15, and CO oxidation activity was also improved.

Application of Ozone Oxidation to Reduce the Biological Treatment Time of Petrochemical Wastewater (석유화학 폐수의 생물학적 처리시간 단축을 위한 오존 산화의 적용)

  • Hong, Eun-Sik;Kim, Hyun-Suk;Lee, Sang-Hee;Chung, Jin-Suk;Shin, Eun-Woo;Ryu, Keun-Garp;Yoo, Ik-Keun
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.5
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    • pp.573-576
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    • 2006
  • The efficacy of integrated ozone oxidation-biodegradation treatment was examined in the treatment of petrochemical wastewater with a special focus on the overall treatment time. When raw wastewater with chemical oxygen demand(COD) of 70-80 mg/L was oxidized by ozone, approximately 20% of initial COD was removed in less than 1.5 min at a dosing rate of 400 mg $O_3/L{\cdot}h $. No further decrease in COD was observed for the extended ozone treatment up to 30 min. Biological treatment alone showed a rapid reduction of COD to 40-50 mg/L, subsequently resulting in the decreased rate of COD removal. Pre-treatment by ozone before biological treatment did not significantly affect the specific rate of COD removal in a biological treatment. When ozone oxidation followed biological treatment, the extent of COD removal by ozone oxidation was greater compared to that of biologically-treated wastewater for a shorter time. Taken together, it was decided that the biological treatment time could be reduced if the treatment processes of concern will be properly arranged.

Interaction Metal Ions with NADH Model Compounds. Cupric Ion Oxidation of Dihydronicotinamides

  • Park, Joon-Woo;Yun, Sung-Hoe;Koh Park, Kwang-Hee
    • Bulletin of the Korean Chemical Society
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    • v.9 no.5
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    • pp.298-303
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    • 1988
  • Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.