• 제목/요약/키워드: In-situ chemical oxidation

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Cyclohexane Oxidations by an Iron-Palladium Bicatalytic System; Soluble Catalysts and Polymer Supported Catalysts

  • Jun, Gi Won;Sim, Eun Gyeong;Park, Sang Eon;Lee, Gyu Wan
    • Bulletin of the Korean Chemical Society
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    • v.16 no.5
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    • pp.398-400
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    • 1995
  • Selective oxidation of cyclohexane in acetone solution has been studied using iron catalysts with hydrogen peroxide in-situ produced by palladium catalyst. Iron tetraphenylporphyrin chloride shows the highest activity among the tested chlorides and porphyrin complexes of some metals of the first transiton series. Iron chloride and iron tetraphenylporphyrin chloride were supported on four kinds of 4-vinylpyridine copolymer with styrene or divinyl-benzene. Nitrogen 1s photoelectron spectra give the evidence that pyridyl nitrogens of the 4-vinyl pyridine copolymer act as ligands to bind iron species. The copolymer with styrene is the most efficient support for the binding because its solubility in catalyst preparation solvent (methylene chloride) gives the pyridyl group advantage to contact with the iron catalysts. However, better catalytic activity per iron atom could be obtained with a rigid crosslinked polymer due to active site isolation.

Influence of Reactivity of Reinforcing Nanoparticles with Aqueous Solution on Electroplating Copper Films (강화상 나노입자의 용액 반응성이 구리 도금 박막에 미치는 영향)

  • Park, Jieun;Oh, Minju;Kim, Yiseul;Lee, Dongyun
    • Korean Journal of Materials Research
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    • v.23 no.12
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    • pp.695-701
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    • 2013
  • To understand how reactivity between reinforcing nanoparticles and aqueous solution affects electrodeposited Cu thin films, two types of commercialized cerium oxide (ceria, $CeO_2$) nanoparticles were used with copper sulfate electrolyte to form in-situ nanocomposite films. During this process, we observed variation in colors and pH of the electrolyte depending on the manufacturer. Ceria aqueous solution and nickel sulfate ($NiSO_4$) aqueous solutions were also used for comparison. We checked several parameters which could be key factors contributing to the changes, such as the oxidation number of Cu, chemical impurities of ceria nanoparticles, and so on. Oxidation number was checked by salt formation by chemical reaction between $CuSO_4$ solution and sodium hydroxide (NaOH) solution. We observed that the color changed when $H_2SO_4$ was added to the $CuSO_4$ solution. The same effect was obtained when $H_2SO_4$ was mixed with ceria solution; the color of ceria solution changed from white to yellow. However, the color of $NiSO_4$ solution did not show any significant changes. We did observe slight changes in the pH of the solutions in this study. We did not obtain firm evidence to explain the changes observed in this study, but changes in the color of the electrolyte might be caused by interaction of Cu ion and the by-product of ceria. The mechanical properties of the films were examined by nanoindentation, and reaction between ceria and electrolyte presumably affect the mechanical properties of electrodeposited copper films. We also examined their crystal structures and optical properties by X-ray diffraction (XRD) and UV-Vis spectroscopy.

Preparation of Honeycomb-patterned Polyaniline-MWCNT/Polystyrene Composite Film and Studies on DC Conductivity

  • Kim, Won-Jung;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2345-2351
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    • 2012
  • Conductive honeycomb-patterned polystyrene (PS) thin films were prepared by the formation of a polyaniline (PANI) thin layer on the surface of the patterned PS thin films using simple one-step chemical oxidative polymerization of aniline. The in situ chemical oxidation polymerization of aniline hydrochloride solution on the patterned structure of the PS films was conducted in the presence of multiwalled carbon nanotubes (MWCNT) to prepare the PANI-MWCNT/PS composite film. The concentration (wt %) of MWCNT was varied in the range of 1%-3% by weight. The dependence of surface morphology of the PANI/PS and PANI-MWCNT/PS composite film to the polymerization time was observed by scanning electron microscopy. The room temperature DC conductivity was obtained by the four-probe technique. The conductivity of the PANI-MWCNT/PS composite film was affected both by the MWCNT concentration and polymerization time. In addition, DC electrical field was loaded during the oxidative polymerization to affect the distribution of the MWCNT included in the composite film, varying the loading voltage in the range of 0.1-3.0 V. The conductivity of the PANI-MWCNT/PS composite film was increased as loading voltage rose. However, this increase stops at a voltage higher than the critical value.

Oxidation of Benzyl Ethers in Sodium Hypochlorite Mediated Piperidine-1-oxyl System (촉매량의 Piperidine-1-oxyl과 NaOCl계에서 벤질 에테르 유도체들의 산화 반응)

  • Cho, Nam Sook;Park, Chan Heun
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.657-665
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    • 1995
  • The oxidation of various benzyl ethers and benzyl alkyl ethers to benzoates has been studied in two-phase system of $CH_3CO_2Et$ and aqueous NaOCl (6.6 mol eq.). The oxidant N-oxo-4-methoxy-2,2,6,6-tetramethylpiperidium bromide (N-oxoammonium salt) was prepared in situ and recycled by addition of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (0.03 mol eq., 4-methoxy-TEMPO), co-catalyst KBr (0.03mol eq.) and second oxidant NaOCl. Thus the catalytic amount of 4-methoxy-TEMPO was used. An adjustment of the pH value of below 8.0 was also required for this reaction with 2.5 hr of reaction time at 0∼5$^{\circ}C$. Under these conditions benzyl ethers were oxidized to benzoates. The selectivity of oxidation of benzyl alkyl ethers is dependent on the acidity of hydrogen and steric effect of alkyl group.

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Nanohybridization of Polyoxometalate and Nanomaterials for Electrochemical Application (전기 화학 응용을 위한 폴리옥소메탈레이트와 나노물질의 나노하이브리드화)

  • Yang, MinHo;Choi, Bong Gill
    • Applied Chemistry for Engineering
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    • v.29 no.4
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    • pp.363-368
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    • 2018
  • Polyoxometalates (POMs) have outstanding properties and a great deal of potential for electrochemical applications. As POMs are highly soluble, the implementation of POMs in various functional materials is required to fully use their potential in electrochemical devices. Here, we will review the recently developed immobilization methods to incorporate POMs into conductive nanomaterials, such as nanocarbons and conducting polymers. Various immobilization strategies involve POMs entrapped in conducting polymer matrix and integration of POMs into nanocarbons using a Langmuir-Blodgett technique, a layer-by-layer self-assembly, and an electrochemical in-situ polymerization. In addition, we will review a variety of electrochemical applications including electrocatalysts for water oxidation, lithium-ion batteries, supercapacitors, and electrochemical biosensors.

An Electro-Fenton System Using Magnetite Coated One-body Catalyst as an Electrode (일체형 산화철 촉매를 전극으로 하는 전기펜톤산화법)

  • Choe, Yun Jeong;Ju, Jeh Beck;Kim, Sang Hoon
    • Applied Chemistry for Engineering
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    • v.29 no.1
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    • pp.117-121
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    • 2018
  • A stainless steel mesh was applied to the cathode of an electro-Fenton system. Methylene blue (MB) solution was chosen as the model waste water with non-biodegradable pollutants. For the model waste water, the degradation efficiency was compared among various SUS mesh cathodes with different surface treatments and magnetite coatings on them. With increasing amount of the magnetite coating on SUS mesh, the degradation efficiency also increased. The improved electro-catalytic characteristic was explained by the increased amount of in situ generated hydrogen peroxide near the cathode surface. Cyclic voltammetry data also showed improved electro-catalytic performance for SUS mesh with more magnetite coatings on them.

Control of Persulfate Activation Rate and Improvement of Active Species Transfer Rate Using Selenium-modified ZVI (셀레늄으로 개질된 영가철을 이용한 과황산 활성화 속도 조절 및 활성종 전달율 향상에 관한 연구)

  • Hee-won Kwon;Hae-Seong Park;In-seong Hwang;Jeong-Jin Kim;Young-Hun Kim
    • Journal of Environmental Science International
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    • v.32 no.1
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    • pp.57-65
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    • 2023
  • The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

Simultaneous Control of Phase Transformation and Crystal of Amorphous TiO2 Coating on MWCNT Surface

  • Cha, Yoo Lim;Park, Il Han;Moon, Kyung Hwan;Kim, Dong Hwan;Jung, Seung Il;Yoon, Young Soo
    • Journal of the Korean Ceramic Society
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    • v.55 no.6
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    • pp.618-624
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    • 2018
  • We developed a mass production method that simultaneously controls the phase transformation and crystal size of $TiO_2$ coatings on multiwalled carbon nanotubes (MWCNTs). Initially, MWCNTs were successfully coated with amorphous 15-20-nm-thick $TiO_2$ by an in-situ sol-gel method. As the calcination temperature increased in both air and argon atmospheres, the amorphous $TiO_2$ was gradually transformed into the fully anatase phase at approximately $600^{\circ}C$, a mixture of the anatase and rutile phases at approximately $700^{\circ}C$, and the fully rutile phase above approximately $800^{\circ}C$. The crystal size increased with increasing calcination temperature. Moreover, above $600^{\circ}C$, the size of crystals formed in air was approximately twice that of crystals formed in argon. The reason is thought to be that MWCNTs, which continuously supported the stresses associated with the reconstructive phase transformation, disappeared owing to complete oxidation in air at these high temperatures.

Application of Galvanic Oxidation and Pyrite Dissolution for Sustainable In-Situ Mine Tailings Treatment (갈바닉 산화와 황철석 용해를 이용한 친환경 원위치 광미 무해화 기술)

  • Ju, Won Jung;Jho, Eun Hea;Nam, Kyoungphile
    • Ecology and Resilient Infrastructure
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    • v.3 no.4
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    • pp.279-284
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    • 2016
  • Mine tailings generated during mining activity often contain high concentrations of heavy metals, with pyrite-containing mine tailings in particular being a major cause of environmental problems in mining areas. Chemical cell technology, or fuel cell technology, can be applied to leach heavy metals in pyrite-containing mine tailings. As pyrite dissolves through spontaneous oxidation (i.e. galvanic oxidation) in the anode compartment of the cell, $Fe^{3+}$, sulfuric acid are generated. A decrease in pH due to the generation of sulfuric acid allows heavy metals to be leached from pyrite-containing mine tailings. In this study, pyrite was dissolved for 4 weeks at $23^{\circ}C$ in an acidic solution (pH 2) and in a galvanic reactor, which induces galvanic oxidation, and total Fe leached from pyrite and pH were compared in order to investigate if galvanic oxidation can facilitate pyrite oxidation. The change in the pyrite surface was analyzed using a scanning electron microscope (SEM). Comparing the total Fe leached from the pyrite, there were 2.9 times more dissolution of pyrite in the galvanic reactor than in the acidic solution, and thus pH was lower in the galvanic reactor than in the acidic solution. Through SEM analysis of the pyrite that reacted in the galvanic reactor, linear-shaped cracks were observed on the surface of the pyrite. The study results show that pyrite dissolution was facilitated through the galvanic oxidation in the galvanic reactor, and also implied that the galvanic oxidation can be one remediation option for pyrite-containing mine tailings.

A Study on the Characteristics of a Pt/TiO2 Catalyst Prepared by Liquid-Phase Ruduction for Formaldehyde Oxidation at Room Temperature (액상환원 기반 Pt/TiO2 촉매 제조를 이용한 포름알데히드 상온 산화 반응 특성 연구)

  • Jae Heon Kim;Younghee Jang;Geo Jong Kim;Sung Chul Kim;Sung Su Kim
    • Applied Chemistry for Engineering
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    • v.34 no.6
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    • pp.613-618
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    • 2023
  • Modern society spends more than 80% of its daily life indoors, emphasizing the need for attention to indoor air pollution due to the improvement in living standards. In this study, the performance and reaction characteristics of the Pt/TiO2 catalysts prepared by liquid-phase reduction for the removal of formaldehyde (HCHO), one of the indoor air pollutants, at room temperature without the need for additional light or heat were investigated. As a result, it showed that catalysts prepared by the same method showed approximately 40~80% various activities depending on the type of TiO2. XRD, BET, and XPS analyses were performed to investigate the particle size, crystal structure, specific surface area, and O/Ti molar ratio of the support material, and it revealed that the correlation between the properties and performance was insignificant. To explore the oxidation reaction pathway of formaldehyde (HCHO), in situ DRIFT analysis using carbon monoxide and H2-TPR was perfomed. The results revealed that the performance was demonstrated by the oxidation state of the active metal and the adsorption-desorption characteristics of the adsorbate species.