• Title/Summary/Keyword: metal catalysis

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Metal-Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Thionobenzoate: Effects of Modification of Electrophilic Center from C=O to C=S

  • Um, Ik-Hwan;Song, Yoon-Ju;Kim, Min-Young;Lee, Jae-In
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1525-1529
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    • 2013
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

Electrochemical Synthesis of Metal-organic Framework (전기화학적 방법을 통한 금속 유기 골격체 합성)

  • Moon, Sanghyeon;Kim, Jiyoung;Choi, Hyun-Kuk;Kim, Moon-Gab;Lee, Young-Sei;Lee, Kiyoung
    • Applied Chemistry for Engineering
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    • v.32 no.3
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    • pp.229-236
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    • 2021
  • During the last two decades, metal-organic frameworks (MOFs) have been drawn attention due to their high specific surface area, porosity, and catalytic activities that allow to use in many applications such as sensor, catalysis, energy storage, etc. To synthesize MOFs hydrothermal or solvothermal method were generally used. However, these methods require high-cost equipment and long time-spend for the synthesis with multi-step process. In contrast, electrochemical synthesis has been considered as a simple and easy process under the ambient conditions. In this review, we described the mechanism of electrochemical MOFs synthesis by the number of configured electrodes system, with the recent reports of various applications.

Practical Usage of Low-Temperature Metal Catalyst for the Destruction of Volatile Organic Compounds (VOCs) (휘발성 유기화합물(VOCs) 제거를 위한 저온금속촉매 실용화에 관한 연구)

  • Jung, Sung-Chul;Lee, Seung-Hwan
    • Journal of Korean Society of Environmental Engineers
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    • v.34 no.6
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    • pp.397-405
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    • 2012
  • In this study, performance evaluation of newly developed technology for the economical and safe removal of volatile organic compounds (VOCs) coming out from electronic devices washing operation and offensive odor induction materials was made. Metal oxidization catalyst has shown 50% of removal efficiency at the temperature of $220^{\circ}C$. Composite metal oxidization catalyst applied in this study has shown that the actual catalysis has started at the temperature of $100^{\circ}C$. Comprehensive analysis on the catalyst property using Mn-Cu metal oxidization catalyst in the pilot-scale unit was made and the removal efficiency was variable with temperature and space velocity. Full-scale unit developed based on the pilot-scale unit operation has shown 95% of removal efficiency at the temperature of $160^{\circ}C$. Optimum elimination effective rates for the space velocity was found to be $6,000hr^{-1}$. The most appropriate processing treatment range for the inflow concentration of VOCs was between 200 ppm to 4,000 ppm. Catalyst control temperature showed high destruction efficiency at $150{\sim}200^{\circ}C$ degrees Celsius in 90~99%. External heat source was not necessary due to the self-heat reaction incase of VOCs inflow concentration is more than 1,000 ppm. Equipment and fuel costs compared to the conventional RTO/RCO method can be reduced by 50% and 75% respectively. And it was checked when there was poisoning for sulfide and acid gas.

Adsorption and Storage of Natural Gas by Nanoporous Adsorbents (나노세공체 흡착제에 의한 천연가스의 흡착 및 저장)

  • Jhung, Sung Hwa;Chang, Jong-San
    • Applied Chemistry for Engineering
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    • v.20 no.2
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    • pp.117-125
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    • 2009
  • In order to utilize natural gas (NG), one of the clean energy sources in next-generation, as a fuel for vehicles, it is important to store natural gas with high density. To store NG by adsorption (ANG) at room temperature and at relatively low pressure(35~40 atm) is safe and economical compared with compressed NG and liquefied NG. However, so far no adsorbent is reported to have adsorption capacity suitable for commercial applications. Nanoporous materials including metal-organic frameworks can be potential adsorbents for ANG. In this review, physicochemical properties of adsorbents necessary for high adsorption capacity are summarized. Wide surface area, large micropore volume, suitable pore size and high density are necessary for high energy density. Moreover, low adsorption-desorption energy, rapid adsorption-desorption kinetics and high delivery are needed. Recently, various efforts have been reported to utilize nanoporous materials in ANG, and it is expected to develop a nanoporous material suitable for ANG.

Chemistry of persulfates for the oxidation of organic contaminants in water

  • Lee, Changha;Kim, Hak-Hyeon;Park, Noh-Back
    • Membrane and Water Treatment
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    • v.9 no.6
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    • pp.405-419
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    • 2018
  • Persulfates (i.e., peroxymonosulfate and peroxydisulfate) are capable of oxidizing a wide range of organic compounds via direct reactions, as well as by indirect reactions by the radical intermediates. In aqueous solution, persulfates undergo self-decomposition, which is accelerated by thermal, photochemical and metal-catalyzed methods, which usually involve the generation of various radical species. The chemistry of persulfates has been studied since the early twentieth century. However, its environmental application has recently gained attention, as persulfates show promise in in situ chemical oxidation (ISCO) for soil and groundwater remediation. Persulfates are known to have both reactivity and persistence in the subsurface, which can provide advantages over other oxidants inclined toward either of the two properties. Besides the ISCO applications, recent studies have shown that the persulfate oxidation also has the potential for wastewater treatment and disinfection. This article reviews the chemistry regarding the hydrolysis, photolysis and catalysis of persulfates and the reactions of persulfates with organic compounds in aqueous solution. This article is intended to provide insight into interpreting the behaviors of the contaminant oxidation by persulfates, as well as developing new persulfate-based oxidation technologies.

Fabrication of Pd/NiCr gate MISFET sensor for detecting hydrogen dissolved in Oil. (유중 용존수소 감지를 위한 Pd/NiCr 게이트 MISFET 센서의 제작)

  • Kim, Gop-Sick;Lee, Jae-Gon;Hahm, Sung-Ho;Choi, Sie-Young
    • Journal of Sensor Science and Technology
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    • v.6 no.3
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    • pp.221-227
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    • 1997
  • The Pd/NiCr gate MISFET-type sensors were fabricated for detecting hydrogen dissolved in high-capacivity transformer oil. To improve stability and high concentration sensitivity of the sensor, Pd/NiCr double catalysis metal gate was used. To reduce the serious gate voltage drift of the sensor induced by hydrogen, the gate insulators of 2 FETs were constructed with double layer of silicon dioxide and silicon nitride. The hydrogen sensitivity of the Pd/NiCr gate MISFET is about a half of Pd/Pt gate MISFET's sensitivity but the Pd/NiCr gate MISFET has good stability and high concentration detectivity up to 1000 ppm.

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Weathering of coal and kerogen : implications on the geochmical carbon and oxygen cycle and the environmental geochemical reactions (탄질 유기물과 케로젠의 풍화 : 탄소와 산소의 지화학적 순환 및 환경화학적 반응에 미치는 영향)

  • 장수범
    • Economic and Environmental Geology
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    • v.32 no.1
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    • pp.101-111
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    • 1999
  • Sedimentary organic matter, exposed to continental surficial environment, reacts with oxygen supplied from the atmosphee and forms carbon-containing oxidation products. Knowledge of the rate and mechanisms of sedimentary organic matter weathering is important because it is one of the major controls on atmospheric oxygen level through geologic time. Under the abiological conditions, the oxidation rate of coal organic matter by molecular oxygen is enhanced by the increase of oxygen concentration and temperature. At ambient temperature and pressure, aqueous coal oxidation results in the formation of dissolved $CO_2$ dissolved organic carbon and solid oxidation products which are all quantitatively significant reaction products. The effects of pH, ultraviolet light, and microbial activity on the weathering of sedimentary organic matter are poorly contrained. Based on the results of geochmical and environmental studies, it is believed that the photochemical reaction should play an important role in the decomposition and oxidation of sedimentary organic matter removed from the weathering profile. At higher pH conditions, the production rate of DOC can be accelerated due to base catalysis. These high molecular weight oranic matter can react with man-made pollutants such as heavy metal ions via adsorption/desorption or ion exchange reactions. The effect of microbial activity on the oxidative weathering of sedimentary organic matter is poorly understood and remains to be studied.

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Development of a Enamel Coating Machine Typed VOC Incineration and Flue Gas Recirculation (VOC 소각 및 연소가스 재 순환 에나멜 도장장치 개발)

  • 정남조;유인수;유상필;송광섭
    • Proceedings of the Korea Society for Energy Engineering kosee Conference
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    • 2003.05a
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    • pp.579-587
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    • 2003
  • A lot of VOCs that is noxious ate exhausted at drying process of enamel coating device. This VOC gas can be incinerated perfectly through catalytic combustion, and heat that is occurred in incineration process ran be again used in drying process. By using VU catalytic combustion technology, in this study, we developed a enamel coating machine that have an excellent environment improvement and energy saying effect. As basic research for this development characteristics ana performance of catalytic combustion for VOC gas was evaluated and numerical analysis for drying oven was calculated. According to the result, VOCs combustion characteristics of metal form catalysis was excellent in high temperature, and it was seen that enamel coating machine should be designed as a precious controllable structure of recirculating supply rate and suction rate.

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Reaction Route to the Crystallization of Copper Oxides

  • Chen, Kunfeng;Xue, Dongfeng
    • Applied Science and Convergence Technology
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    • v.23 no.1
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    • pp.14-26
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    • 2014
  • Copper is an important component from coin metal to electronic wire, integrated circuit, and to lithium battery. Copper oxides, mainly including $Cu_2O$ and CuO, are important semiconductors for the wide applications in solar cell, catalysis, lithium-ion battery, and sensor. Due to their low cost, low toxicity, and easy synthesis, copper oxides have received much research interest in recent year. Herein, we review the crystallization of copper oxides by designing various chemical reaction routes, for example, the synthesis of $Cu_2O$ by reduction route, the oxidation of copper to $Cu_2O$ or CuO, the chemical transformation of $Cu_2O$ to CuO, the chemical precipitation of CuO. In the designed reaction system, ligands, pH, inorganic ions, temperature were used to control both chemical reactions and the crystallization processes, which finally determined the phases, morphologies and sizes of copper oxides. Furthermore, copper oxides with different structures as electrode materials for lithium-ion batteries were also reviewed. This review presents a simple route to study the reaction-crystallization-performance relationship of Cu-based materials, which can be extended to other inorganic oxides.

Recent advances of aromatic C-F bond borylation and its application to positron emission tomography

  • Song, Dalnim;Lee, Sanghee;Lee, Byung Chul;Kim, Sang Eun;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.1 no.2
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    • pp.80-87
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    • 2015
  • Carbon-fluorine (C-F) bonds have been found ubiquitously in pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science due to their unique properties such as thermal and oxidative stability and lipophilicity to improve bioavailability. For the past five years, there have been significant advances in F-18 fluorination of aromatic complex molecules combined with the development of late-stage fluorination reactions. More recently, direct incorporation of F-18 to fluorinated aromatic molecules via borylation of C-F bonds has been developed by Niwa and Hosoya. In this minireview, we will discuss the progress of C-F bondborylation of fluorinated arenes utilizing transition metal catalysts and the impact on the development of F-18 radiotracers for positron emission tomography (PET).