• Title/Summary/Keyword: Catalytic Oxidation

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Integrated Microdisk Gold Electrode Modified with Metal-porphyrin and Metal-phthalocyanines for Nitric Oxide Determination in Biological Media

  • Kim, Il-Kwang;Bae, Hyun-Ok;Oh, Gi-Soo;Chung, Hun-Taeg;Kim, Young-Jin;Chun, Hyun-Ja
    • Bulletin of the Korean Chemical Society
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    • v.24 no.11
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    • pp.1579-1584
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    • 2003
  • An integrated gold microdisk electrode was constructed and modified with metal-porphyrin or metal-phthalocyanines for NO determination in biological media. Microanalysis of NO using square wave anodic stripping voltammetry in $1\;{\times}\;10^{-2}$ M $HClO_4$ was optimal when the accumulation potential was 0.1 V, frequency 100 Hz, and the scan rate was 200 mV/s. When the electrode was modified with metal-porphyrin or metal-phthalocyanines, the anodic peak currents of NO increased due to the catalytic oxidation of NO. In case of Fe(II)-phthalocyanine modified electrode, the peak currents remarkably increased and the sensitivity was high. The calibration curve had good linearity in the range from $3.6\;{\times}\;10^{-5}$ M to $7.2\;{\times}\;10^{-7}$ M, and the detection limit was $5.7\;{\times}\;10^{-7}$ M. For the structural stability and increased sensitivity, Fe(II)-phthalocyanine modified gold microdisk electrode coated with Nafion was applied to determination of NO released from cultured macrophase.

Characteristic comparison of sensing materials in mixed potential type NH3 gas sensors for urea-SCR DeNOx system in diesel engine (디젤 엔진 Urea-SCR DeNOx 시스템용 혼합전위 방식 암모니아 가스 센서의 감지물질 특성 비교)

  • Choi, An-Gi;Yang, Young-Chang;Koo, Bon-Chul;Park, C.O.
    • Journal of Sensor Science and Technology
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    • v.19 no.3
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    • pp.176-183
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    • 2010
  • It is considered that the urea injection DeNOx SCR(selective catalytic reduction) system is the only promising method to satisfy the worldwide NOx emission standards. As for the theoretical aspect, reactants of NO and $NO_2$ with $NH_3$ produce $H_2O$, $N_2$ and $O_2$ which do not harm human beings and environmental as well. The realization of maximum NOx conversion (without using a post oxidation catalyst) is only possible with closed loop controlled urea dosing. It means built-in $NH_3$ gas sensor have to be developed for detecting accurate $NH_3$ concentration for the feedback system. Using YSZ(yttria-stabilized zirconia) as a solid state electrolyte and $In_2O_3$ as a sensing material, this paper aims to study dependable $NH_3$ gas sensor for the promising solution of DeNOx technology, which have a reproducible electric output signal, a high sensitivity and fast response.

Identification of an Essential Tryptophan Residue Residue in Alliinase from Garlic (Allium sativum) by Chemical Modification

  • Jin, Yeong Nam;Choe, Yong Hun;Yang, Cheol Hak
    • Bulletin of the Korean Chemical Society
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    • v.22 no.1
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    • pp.68-76
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    • 2001
  • We have employed chemical modification to identify amino acids essential for the catalytic activity of alliinase (EC 4.4.1.4) from garlic (Allium sativum). Alliinase degrades S-alkyl-L cysteine sulfoxides, causing the characteristic odor of garlic. The activity of alliinase was rapidly and completely inactivated by N-bromosuccinimide(NBS) and slightly decreased by succinic anhydride and N-acetylimidazole. These results indicate that tryptophanyl, lysyl, and tyrosyl residues play an important role in enzyme catalysis. The reaction of alliinase with NBA yielded a characteristic decrease in both the absorbance at 280 nm and the intrinsic fluorescence at 332 nm with increasing reagent concentration of NBS, consistent with the oxidation of tryptophan residues. Kinetic analysis, fluorometric titration of tryptophans and correlation to residual alliinase activity showed that modification of only one residue present on alliinase led to complete inhibition of alliinase activity. To identify this essential tryptophan residue, we employed chemical modification by NBS in the presence and absence of the protecting substrate analogue, S-ethyl-L-cysteine (SEC) and N-terminal sequence analysis of peptide fragment isolated by reverse phase-HPLC. A fragment containing residues 179-188 was isolated. We conclude that Trp182 is essential for alliinase activity.

Implementation of magnetic Fe3O4@ZIF-8 nanocomposite to activate sodium percarbonate for highly effective degradation of organic compound in aqueous solution

  • Sajjadi, Saeed;Khataee, Alireza;Soltani, Reza Darvishi Cheshmeh;Bagheri, Nafiseh;Karimi, Afzal;Azar, Amirali Ebadi Fard
    • Journal of Industrial and Engineering Chemistry
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    • v.68
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    • pp.406-415
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    • 2018
  • Here, as-synthesized $Fe_3O_4$ nanoparticles were incorporated into the zeolitic imidazolate framework (ZIF-8) lattice to activate sodium percarbonate (SPC) for degradation of methylene blue (MB). The reaction rate constant of $Fe_3O_4@ZIF-8/SPC$ process ($0.0632min^{-1}$) at acidic conditions (pH = 3) was more than six times that of the $Fe_3O_4/SPC$ system ($0.009min^{-1}$). Decreasing the solute concentration, along with increasing SPC concentration and $Fe_3O_4@ZIF-8$ nanocomposite (NC) dosage, favored the catalytic degradation of MB. The $Fe_3O_4@ZIF-8$ NC after fifteen consecutive treatment processes showed the excellent stability with a negligible drop in the efficiency of the system (<10%). The reaction pathway was obtained via GC-MS analysis.

Effect of activated carbon modified with oxalic acid on the production of IPA from MX catalyzed by H3PW12O40@carbon and cobalt

  • Fang, Zhou-wen;Liu, Hua-jie;Wang, Zhi-hao;Wen, Di;Long, Xiang-li
    • Journal of Industrial and Engineering Chemistry
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    • v.68
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    • pp.87-98
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    • 2018
  • The production of IPA from the oxidation of MX is completed under the catalysis of $H_3PW_{12}O_{40}$ (HPW) loaded on carbon and cobalt. Oxalic acid is tried to modify the carbon to upgrade the catalytic activity of HPW@C catalyst. The experiments show that the best carbon is acquired by carbonizing the carbon at $450^{\circ}C$ for 2 h in $N_2$ after being soaked in a $0.20mol\;l^{-1}$ oxalic acid solution for 16 h. The IPA produced by the HPW@C catalysts prepared with the carbon modified is 58.9% over that obtained by the catalysts prepared with the original carbon.

Chemical Poisoning of Ni/MgO Catalyst by Alkali Carbonate Vapor in the Steam Reforming Reaction of DIR-MCFC

  • 문형대;임태훈;이호인
    • Bulletin of the Korean Chemical Society
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    • v.20 no.12
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    • pp.1413-1417
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    • 1999
  • Chemical poisoning of Ni/MgO catalyst was induced by hot alkali carbonate vapor in molten carbonate fuel cell (MCFC), and the poisoned (or contaminated) catalyst was characterized by TPR/TPO, FTIR, and XRD analysis. Carbonate electrolytes such as K and Li were transferred to the catalyst during DIR-MCFC operation at 650 ℃. The deposition of alkali species on the catalyst consequently led to physical blocking on catalytic active sites and structural deformation by chemical poisoning. TPR/TPO analysis indicated that K species enhanced the reducibility of NiO thin film over Ni as co-catalyst, and Li species lessened the reducibility of metallic Ni by chemical reaction with MgO. FTIR analysis of the poisoned catalyst did not exhibit the characteristic ${\vector}_1$$(D_{3h})$ peaks (1055 $cm^{-1},\;1085\;cm{-1})$ for pure crystalline carbonates, instead a new peak (1120 $cm^{-1})$ was observed proportionally with deformed alkali carbonates. From XRD analysis, the oxidation of metallic Ni into $Ni_xMg_{1-x}O$ was confirmed by the peak shift of MgO with shrinking of Ni particles. Conclusively, hot alkali species induced both chemical poisoning and physical deposition on Ni/MgO catalyst in DIR-MCFC at 650 ℃.

Hydrophobicity in nanocatalysis

  • Alimoradlu, Khadijeh;Zamani, Asghar
    • Advances in nano research
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    • v.12 no.1
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    • pp.49-63
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    • 2022
  • Nanocatalysts are usually used in the synthesis of petrochemical products, fine chemicals, biofuel production, and automotive exhaust catalysis. Due to high activity and stability, recyclability, and cost-effectiveness, nanocatalysts are a key area in green chemistry. On the other hand, water as a common by-product or undesired element in a range of nanocatalyzed processes may be promoting the deactivation of catalytic systems. The advancement in the field of hydrophobicity in nanocatalysis could relatively solves these problems and improves the efficiency and recyclability of nanocatalysts. Some recent developments in the synthesis of novel nanocatalysts with tunable hydrophilic-hydrophobic character have been reviewed in this article and followed by highlighting their use in catalyzing several processes such as glycerolysis, Fenton, oxidation, reduction, ketalization, and hydrodesulfurization. Zeolites, carbon materials, modified silicas, surfactant-ligands, and polymers are the basic components in the controlling hydrophobicity of new nanocatalysts. Various characterization methods such as N2 adsorption-desorption, scanning and transmission electron microscopy, and contact angle measurement are critical in the understanding of hydrophobicity of materials. Also, in this review, it has been shown that how the hydrophobicity of nanocatalyst is affected by its structure, textural properties, and surface acidity, and discuss the important factors in designing catalysts with high efficiency and recyclability. It is useful for chemists and chemical engineers who are concerned with designing novel types of nanocatalysts with high activity and recyclability for environmentally friendly applications.

Photocatalytic Oxidation of Arsenite Using Goethite and UV LED (침철석과 자외선 LED를 이용한 아비산염의 광촉매 산화)

  • Jeon, Ji-Hun;Kim, Seong-Hee;Lee, Sang-Woo;Kim, Soon-Oh
    • Journal of Korean Society of Environmental Engineers
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    • v.39 no.1
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    • pp.9-18
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    • 2017
  • Arsenic (As) has been considered as the most toxic one among various hazardous materials and As contamination can be caused naturally and anthropogenically. Major forms of arsenic in groundwater are arsenite [(As(III)] and/or arsenate [(As(V)], depending on redox condition: arsenite and arsenate are predominant in reduced and oxidized environments, respectively. Because arsenite is much more toxic and mobile than arsenate, there have been a number of studies on the reduction of its toxicity through oxidation of As(III) to As(V). This study was initiated to develop photocatalytic oxidation process for treatment of groundwater contaminated with arsenite. The performance of two types of light sources (UV lamp and UV LED) was compared and the feasibility of goethite as a photocatalyst was evaluated. The highest removal efficiency of the process was achieved at a goethite dose of 0.05 g/L. Based on the comparison of oxidation efficiencies of arsenite between two light sources, the apparent performance of UV LED was inferior to that of UV lamp. However, when the results were appraised on the basis of their emitting UV irradiation, the higher performance was achieved by UV LED than by UV lamp. This study demonstrates that environmentally friendly process of goethite-catalytic photo-oxidation without any addition of foreign catalyst is feasible for the reduction of arsenite in groundwater containing naturally-occurring goethite. In addition, this study confirms that UV LED can be used in the photo-oxidation of arsenite as an alternative light source of UV lamp to remedy the drawbacks of UV lamp, such as long stabilization time, high electrical power consumption, short lifespan, and high heat output requiring large cooling facilities.

Removal of Nitrogen Oxides Using Hydrocarbon Selective Catalytic Reduction Coupled with Plasma (플라즈마가 결합된 탄화수소 선택적 촉매환원 공정에서 질소산화물(NOx)의 저감)

  • Ihm, Tae Heon;Jo, Jin Oh;Hyun, Young Jin;Mok, Young Sun
    • Applied Chemistry for Engineering
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    • v.27 no.1
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    • pp.92-100
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    • 2016
  • Low-temperature conversion of nitrogen oxides using plasma-assisted hydrocarbon selective catalytic reduction of (HC-SCR) was investigated. Plasma was created in the catalyst-packed bed so that it could directly interact with the catalyst. The effect of the reaction temperature, the shape of catalyst, the concentration of n-heptane as a reducing agent, the oxygen content, the water vapor content and the energy density on $NO_x$ removal was examined. $NO_x$ conversion efficiencies achieved with the plasma-catalytic hybrid process at a temperature of $250^{\circ}C$ and an specific energy input (SIE) of $42J\;L^{-1}$ were 83% and 69% for one-dimensional Ag catalyst ($Ag\;(nanowire)/{\gamma}-Al_2O_3$) and spherical Ag catalyst ($Ag\;(sphere)/{\gamma}-Al_2O_3$), respectively, whereas that obtained with the catalyst-alone was considerably lower (about 30%) even with $Ag\;(nanowire)/{\gamma}-Al_2O_3$ under the same condition. The enhanced catalytic activity towards $NO_x$ conversion in the presence of plasma can be explained by the formation of more reactive $NO_2$ species and partially oxidized hydrocarbon intermediates from the oxidation of NO and n-heptane under plasma discharge. Increasing the SIE tended to improve $NO_x$ conversion efficiency, and so did the increase in the n-heptane concentration; however, a further increase in the n-heptane concentration beyond $C_1/NO_x$ ratio of 5 did not improve the $NO_x$ conversion efficiency any more. The increase in the humidity affected negatively the $NO_x$ conversion efficiency, resulting in lowering the $NO_x$ conversion efficiency at the higher water vapor content, because water molecules competed with $NO_x$ species for the same active site. The $NO_x$ conversion efficiency increased with increasing the oxygen content from 3 to 15%, in particular at low SIE values, because the formation of $NO_2$ and partially oxidized hydrocarbon intermediates was facilitated.

Dry reforming of Propane to Syngas over Ni-CeO2/γ-Al2O3 Catalysts in a Packed-bed Plasma Reactor (충전층 플라즈마 반응기에서 Ni-CeO2/γ-Al2O3 촉매를 이용한 프로페인-합성 가스 건식 개질)

  • Sultana, Lamia;Rahman, Md. Shahinur;Sudhakaran, M.S.P.;Hossain, Md. Mokter;Mok, Young Sun
    • Clean Technology
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    • v.25 no.1
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    • pp.81-90
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    • 2019
  • A dielectric barrier discharge (DBD) plasma reactor packed with $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst was used for the dry ($CO_2$) reforming of propane (DRP) to improve the production of syngas (a mixture of $H_2$ and CO) and the catalyst stability. The plasma-catalytic DRP was carried out with either thermally or plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst at a $C_3H_8/CO_2$ ratio of 1/3 and a total feed gas flow rate of $300mL\;min^{-1}$. The catalytic activities associated with the DRP were evaluated in the range of $500{\sim}600^{\circ}C$. Following the calcination in ambient air, the ${\gamma}-Al_2O_3$ impregnated with the precursor solution ($Ni(NO_3)_2$ and $Ce(NO_3)_2$) was subjected to reduction in an $H_2/Ar$ atmosphere to prepare $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst. The characteristics of the catalysts were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectrometry (EDS), temperature programmed reduction ($H_2-TPR$), temperature programmed desorption ($H_2-TPD$, $CO_2-TPD$), temperature programmed oxidation (TPO), and Raman spectroscopy. The investigation revealed that the plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst exhibited superior catalytic activity for the production of syngas, compared to the thermally reduced catalyst. Besides, the plasma-reduced $Ni-CeO_2/{\gamma}-Al_2O_3$ catalyst was found to show long-term catalytic stability with respect to coke resistance that is main concern regarding the DRP process.