• Title/Summary/Keyword: Redox active

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Characteristics of Pd Catalysts for Methane Oxidation (메탄 산화를 위한 Pd 촉매의 특성)

  • Lee, Jin-Man;Yang, O-Bong;Kim, Chun-Yeong;Woo, Seong-Ihl
    • Applied Chemistry for Engineering
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    • v.10 no.4
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    • pp.557-562
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    • 1999
  • The reaction properties of Pd. Pd-Ce and Pd-La catalysts supported on ${\gamma}-Al_2O_3$ were investigated in the oxidation reaction of methane($CH_4$) exhausted from the compressed natural gas vehicle in a U-tube flow reactor with gas hourly space velocity of $72,000h^{-1}$. The catalysts were characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), BET surface area and hydrogen chemisorption. Pd catalyst prepared by $Pd(NO_3)_2$ as a palladium precursor and calcined at $600^{\circ}C$ showed the highest activity for a methane oxidation. Catalytic activity of calcined $Pd/{\gamma}-Al_2O_3$ in which most of palladium was converted into palladium oxide species was higher than that of reduced $Pd/{\gamma}-Al_2O_3$ in which most of palladium existed in palladium metal by XRD. As increasing the number of reaction cycles in the wide range of redox, the catalytic activity of $Pd/{\gamma}-Al_2O_3$ was decreased and the highly active window became narrower. Lanthanum oxide promoted Pd catalyst, $Pd/La/{\gamma}-Al_2O_3$ showed enhanced thermal stability compared with $Pd/{\gamma}-Al_2O_3$ even after aging at $1000^{\circ}C$, which was ascribed to the role of La as a promoter to suppress the sintering of palladium metal and ${\gamma}-Al_2O_3$ support. Almost all of methane was removed by the reaction with NO at the redox ratio of 1.2 in case of oxygen excluded steam, but that activity was significantly decreased in the steam containing oxygen.

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Catalytic Activity of Ga(Ⅲ)-, In(Ⅲ)- and Tl(Ⅲ)-porphyrin Complexes (Ga(Ⅲ), In(Ⅲ) 및 Tl(Ⅲ) 금속이온을 포함한 Metalloporphyrin 착물의 촉매적 특성)

  • Park, Yu Chul;Na, Hun Gil;Kim, Seong Su
    • Journal of the Korean Chemical Society
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    • v.39 no.5
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    • pp.364-370
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    • 1995
  • The catalytic oxidations of several olefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin (M=Ga(III), In(III), Tl(III)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were $(p-CH_3O)TPP,\;(p-CH_3)TPP,\;TPP,\;(p-F)TPP,\;(p-Cl)TPP\;and\;(F_20)TPP$ (TPP=tetraphenylporphyrin), and olefins were $(p-CH_3O)-,\;(p-CH_3)-,\;(p-H)-,\;(p-F)-,\;(p-Cl)-\;and\;(p-Br)styrene$styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the ${\sigma}^+$ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(III)- and Tl(III)-porphyrins turned out to be more active catalysts than Ga(III)-porphyrin.

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N2O Decomposition Characteristics and Efficiency Enhancement of Rh/CeO2 Catalyst (Rh/CeO2 촉매의 N2O 분해반응 특성 및 효율증진 연구)

  • Nam, Ki Bok;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.29 no.5
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    • pp.541-548
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    • 2018
  • In this work, the $N_2O$ decomposition catalyst and reaction characteristics to control the $N_2O$ removal were described. Experiments were carried out by using Rh as an active metal catalyst on various supports and the $Rh/CeO_2$ catalyst with $CeO_2$ support showed the best activity for the $N_2O$ decomposition when it was prepared under the constant heat treatment condition ($500^{\circ}C$-4 hr). $H_2-TPR$ and XPS analyzes were performed to confirm the effect of the physical and chemical properties of the catalyst on $N_2O$ decomposition. As a result, it was found that the increase of the oxygen transfer capacity of the catalyst due to the increase of both the redox property and $Ce^{3+}$ amount affected the decomposition reaction of $N_2O$. In addition, the future work will include a treatment process capable of decomposition $N_2O$ and NO under the condition that $N_2O$ and NO are simultaneously generated and its characteristics of $N_2O$ decomposition reaction.

Investigation of Catalytic Deactivation by Small Content Oxygen Contained in Regeneration Gas Influenced on DSRP (직접 황 회수 공정으로 유입되는 재생가스에 함유된 미량산소의 촉매활성저하 원인 규명)

  • Choi, Hee-Young;Park, No-Kuk;Lee, Tae Jin
    • Clean Technology
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    • v.20 no.3
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    • pp.212-217
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    • 2014
  • In order to regenerate the sulfidated desulfurization sorbent, oxygen is used as the oxidant agent on the regeneration process. The small amount of oxygen un-reacted in regeneration process is flowed into direct sulfur recovery process. However, the reactivity for $SO_2$ reduction can be deteriorated with the un-reacted oxygen by various reasons. In this study, the deactivation effects of un-reacted oxygen contained in the off-gas of regeneration process flowed into direct sulfur recovery process of hot gas desulfurization system were investigated. Sn-Zr based catalysts were used as the catalyst for $SO_2$ reduction. The contents of $SO_2$ and $O_2$ contained in the regenerator off-gas used as the reactants were fixed to 5.0 vol% and 4.0 vol%, respectively. The catalytic activity tests with a Sn-Zr based catalyst were for $SO_2$ reduction performed at $300-450^{\circ}C$ and 1-20 atm. The un-reacted oxygen oxidized the elemental sulfur produced by $SO_2$ catalytic reduction and the conversion of $SO_2$ was reduced due to the production of $SO_2$. However, the temperature for the oxidation of elemental sulfur increased with increasing pressure in the catalytic reactor. Therefore, it was concluded that the decrease of reactivity at high pressure is occurred by catalytic deactivation, which is the re-oxidation of lattice oxygen vacancy in Sn-Zr based catalyst with the un-reacted oxygen on the catalysis by redox mechanism. Meanwhile the un-reacted oxygen oxidized CO supplied as the reducing agent and the temperature in the catalyst packed bed also increased due to the combustion of CO. It was concluded that the rapidly increasing temperature in the packed bed can induce the catalytic deactivation such as the sintering of active components.

Electrochemical Immunoassay based on the Dopamine-antigen Conjugate for Detecting Hippuric Acid (항원인 마뇨산에 결합된 도파민을 이용한 전기화학적 면역 분석법)

  • Choi, Young-Bong;Jeon, Won-Yong;Kim, Hyug-Han
    • Journal of the Korean Electrochemical Society
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    • v.17 no.3
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    • pp.172-178
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    • 2014
  • In this work, we describe an electrochemical immunosensor for simple, fast and quantitative detection of a urinary hippuric acid (HA). Urinary HA, of molecular weight 180 DA, is one of the major metabolites and biological indicators in toluene-exposed humans. Simple and ubiquitous monitoring of exposure to toluene is very important in occupational health care. We propose the electrochemical immunoassay based on the dopamine-antigen conjugate for detecting hippuric acid. Our electrochemical immunoassay system employs a conjugate of dopamine (DA) as an electrochemical active molecule and hippuric acid (HA) as an antigen. As an electrochemical aspect, dopamine (DA) containing two hydroxyl group can show excellent redox signal. Also, dopamine-tethered hippuric acid (DA-HA) shows the reversible redox signal in the immunoassay. The competition between HA and DA-HA generated electric signals proportional to HA concentration. The electrochemical immunoassay was performed with DA-HA on the screen printed carbon electrodes (SPCEs), and then applies the mixture antigen (HA) and HA-antibody. The electrical signals were proportional to HA in the range of 0.010~2.500 mg/mL which is enough range to be used for the point-of-care.

Expression, Characterization and Regulation of a Saccharomyces cerevisiae Monothiol Glutaredoxin (Grx6) Gene in Schizosaccharomyces pombe

  • Lee, Jae-Hoon;Kim, Kyunghoon;Park, Eun-Hee;Ahn, Kisup;Lim, Chang-Jin
    • Molecules and Cells
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    • v.24 no.3
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    • pp.316-322
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    • 2007
  • Glutaredoxins (Grxs), also known as thioltransferases (TTases), are thiol oxidoreductases that regulate cellular redox state in a variety of organisms. In the budding yeast Saccharomyces cerevisiae, Grx1 and 2 are cytosolic dithiol Grxs, while Grx3, 4 and 5 are monothiol Grxs. A gene encoding a new monothiol Grx, Grx6, was cloned from the genomic DNA of S. cerevisiae by PCR. Its DNA sequence contains 1,080 bp, and encodes a putative protein of 203 amino acid residues containing Cys-Phe-Tyr-Ser at the active site. Grx6 is similar to other monothiol Grxs in the same organism and to Grx3 in the fission yeast Schizosaccharomyces pombe. and its predicted three-dimensional structure resembles that of S. pombe Grx3. S. pombe cells harboring plasmid pFGRX6 containing the Grx6 gene had about 1.3-fold elevated Grx activity in the exponential phase, and grew better than the control cells under some stressful conditions. Synthesis of ${\beta}$-galactosidase from a Grx6-lacZ fusion gene in S. pombe was enhanced by potassium chloride, aluminum chloride and heat ($37^{\circ}C$) treatment. S. pombe cells harboring plasmid pFGRX6 had elevated ROS levels whereas S. pombe cells harboring extra copies of Grx3 had reduced ROS levels.

Electrochemical and Fluorescent Properties of Ferrocenyl Chalcones Containing 1-Naphthalenyl Group: X-ray Crystal Structure of Fc-C(O)CH=CH-(1-Naph)

  • Suh, Woo-Young;Jeon, Hyo-Kyung;Lee, Ji-Yeon;Lim, Chae-Mi;Lee, Su-Kyung;Noh, Dong-Youn
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.443-448
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    • 2012
  • Ferrocenyl chalcones (Fc-C(O)CH=CH-Ar: Fc-Ar) with mono- and di-1-naphthalenyl moieties (Fc-1Naph and Fc-d1Naph) were prepared and spectroscopically characterized. The enone bridge was in the s-cis conformation and the $\pi$-electrons on the C=C bond were further delocalized on the bridge. The naphthalenyl moiety deviates greatly from the enone-Cp plane by $26.9(1)^{\circ}$. Cyclic voltammetry measurements for Fc-1Naph exhibit one reversible cycle for the redox of the ferrocenyl moiety at a lower potential, and one irreversible oxidation peak at the higher potential region. For Fc-d1Naph, the cyclic voltammogram is more featureless. Fluorescence properties for both compounds are active in polar solvents with $\lambda_{em}$ = 500 nm (EtOH) and $\lambda_{em}$ = 512 nm (MeOH) for Fc-1Naph and $\lambda_{em}$ = 496 nm (EtOH) and $\lambda_{em}$ = 508 nm (MeOH) for Fc-d1Naph. The intensity of Fc-d1Naph is more than twice than that of Fc-1Naph. The fluorescence properties for both compounds are inactive in the less polar solvents such as $CH_3CN$, $CH_2Cl_2$ and $CHCl_3$.

Effects of Ionic Strength, Background Electrolytes, Heavy Metals, and Redox-Active Species on the Reduction of Hexavalent Chromium by Ecklonia Biomass

  • PARK DONGHEE;YUN YEOUNG-SANG;JO JI HYE;PARK JONG MOON
    • Journal of Microbiology and Biotechnology
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    • v.15 no.4
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    • pp.780-786
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    • 2005
  • The biomass of the brown seaweed, Ecklonia, was used to remove Cr(VI) from wastewater. Previously, Cr(VI) was removed through its reduction to Cr(III) when brought into contact with the biomass. In this study, the effects of ionic strength, background electrolytes, and Cr(III), Ni(II), Zn(II), and Fe(III) on the Cr(VI) reduction were examined. An increased ionic strength inhibited the Cr(VI) reduction. The presence of other heavy metals, such as Cr(III), Ni(II), or Zn(II), only slightly affected the Cr(VI) reduction, while Fe(III) enhanced the reduction. Although the above various parameters could affect the reduction rate of Cr(VI) by Ecklonia biomass, these effects were relatively smaller than those of pH and temperature. In addition, the previously derived rate equation was found to be applicable over a range of ionic strengths and with different background electrolytes. In conclusion, Ecklonia, bioniass may be a good candidate as a biosorbent for the removal of Cr(VI) from wastewaters containing various other impurities, and scale-up to a practical process may be accomplished using the previously derived rate equation.

Curcumin Derivatives Inhibit the Formation of Jun-Fos-DNA Complex Independently of their Conserved Cysteine Residues

  • Park, Chi-Hoon;Lee, Ju-Hyung;Yang, Chul-Hak
    • BMB Reports
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    • v.38 no.4
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    • pp.474-480
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    • 2005
  • Curcumin, a major active component of turmeric, has been identified as an inhibitor of the transcriptional activity of activator protein-1 (AP-1). Recently, it was also found that curcumin and synthetic curcumin derivatives can inhibit the binding of Jun-Fos, which are the members of the AP-1 family, to DNA. However, the mechanism of this inhibition by curcumin and its derivatives was not disclosed. Since the binding of Jun-Fos dimer to DNA can be modulated by redox control involving conserved cysteine residues, we studied whether curcumin and its derivatives inhibit Jun-Fos DNA binding activity via these residues. However, the inhibitory mechanism of curcumin and its derivatives, unlike that of other Jun-Fos inhibitors, was found to be independent of these conserved cysteine residues. In addition, we investigated whether curcumin derivatives can inhibit AP-1 transcriptional activity in vivo using a luciferase assay. We found that, among the curcumin derivatives examined, only inhibitors shown to inhibit the binding of Jun-Fos to DNA by Electrophoretic Mobility Shift Assay (EMSA) inhibited AP-1 transcriptional activity in vivo. Moreover, RT-PCR revealed that curcumin derivatives, like curcumin, downregulated c-jun mRNA in JB6 cells. These results suggest that the suppression of the formation of DNA-Jun-Fos complex is the main cause of reduced AP-1 transcriptional activity by curcuminoids, and that EMSA is a suitable tool for identifying inhibitors of transcriptional activation.

Electrochemical Properties of Activated Carbon Supecapacitor Adopting Poly(acrylonitrile) Separator Coated by Polymer-Alkaline Electrolytes (고분자-알칼리 전해질이 코팅된 Poly(acrylonitrile) 분리막을 적용한 활성탄 수퍼커패시터 특성)

  • Kim, Kwang Man;Lee, Young-Gi;Ko, Jang Myoun
    • Korean Chemical Engineering Research
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    • v.55 no.4
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    • pp.467-472
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    • 2017
  • Alkaline electrolytes consisting of 6 M KOH and polymer (PEO, PVA, and PAAK) are coated on PAN nonwoven fabrics as a separator, and the electrochemical properties of the activated carbon supercapacitor adopting them are investigated in terms of redox behavior, specific capacitance, and interfacial impedance. Although the interaction between polymer and KOH are comparatively inactive in PEO and PVA, PAAK (3 wt.%)-KOH forms a hydrogel phase by active interactions between $COO^-K^+$ in side-chain of PAAK and $K^+OH^-$ from alkaline electrolyte solution, improving ionic conduction of electrolytes and the electrochemical properties of the supercapacitor. As a result, the activated supercapacitor adopting the PAAK-KOH shows the superior specific capacitance of $46.8Fg^{-1}$ at $100mVs^{-1}$.