• Title/Summary/Keyword: Oxidation Mechanism

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Molybdenum-Based Electrocatalysts for Direct Alcohol Fuel Cells: A Critical Review

  • Gaurav Kumar Yogesh;Rungsima Yeetsorn;Waritnan Wanchan;Michael Fowler;Kamlesh Yadav;Pankaj Koinkar
    • Journal of Electrochemical Science and Technology
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    • v.15 no.1
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    • pp.67-95
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    • 2024
  • Direct alcohol fuel cells (DAFCs) have gained much attention as promising energy conversion devices due to their ability to utilize alcohol as a fuel source. In this regard, Molybdenum-based electrocatalysts (Mo-ECs) have emerged as a substitution for expensive Pt and Ru-based co-catalyst electrode materials in DAFCs, owing to their unique electrochemical properties useful for alcohol oxidation. The catalytic activity of Mo-ECs displays an increase in alcohol oxidation current density by several folds to 1000-2000 mA mgPt-1, compared to commercial Pt and PtRu catalysts of 10-100 mA mgPt-1. In addition, the methanol oxidation peak and onset potential have been significantly reduced by 100-200 mV and 0.5-0.6 V, respectively. The performance of Mo-ECs in both acidic and alkaline media has shown the potential to significantly reduce the Pt loading. This review aims to provide a comprehensive overview of the bifunctional mechanism involved in the oxidation of alcohols and factors affecting the electrocatalytic oxidation of alcohol, such as synthesis method, structural properties, and catalytic support materials. Furthermore, the challenges and prospects of Mo-ECs for DAFCs anode materials are discussed. This in-depth review serves as valuable insight toward enhancing the performance and efficiency of DAFC by employing Mo-ECs.

The Growth Yield of Desulfovibrio desulfuricans M6 on Different Substrates

  • Park, Doo-Hyun;Shin, Chul-Su;Kim, Byung-Hong;Shin, Pyung-Kyun
    • Journal of Microbiology and Biotechnology
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    • v.6 no.4
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    • pp.232-237
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    • 1996
  • Growth yield of Desulfovibrio desulfuricans M6 was measured using different substrates. The cell yield of fermentative growth on pyruvate was 6.22 g cell $mol^{-l}$ pyruvate. Since 1 ATP is available from substrate-level phosphorylation from the oxidation of pyruvate to acetate, $Y_{ATP}$ of the bacterium should be the same as $Y_{pyruvate}$ (6.22 g cell $mol^{-l}$ ATP). The cell yields of the bacterium on different electron donors were measured with sulfate as the electron acceptor. Cell yields on lactate, pyruvate and $H_2$ were 9.39, 13.76 and 8.45 g cell $mol^{-l}$ substrate, respectively. From these figures ATP available from electron-transport phosphorylation (ETP) of the electron donors used was calculated. ATP produced by ETP of each electron donnor were 1.71 from pyruvate, 1.51 from lactate and 1.76 from $H_2$. These values show that electrons from the oxidation of lactate to pyruvate are consumed to reduce sulfate through a reverse electron transport mechanism requiring 0.2 ATP for each pair of electrons. Based on these results, discussions are made on the electron transport mechanism in the bacterium.

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A Study on the Failure Characteristics of Ceramic Tool for Hardened Steels (경화강에 대한 세라믹공구의 손상특성에 관한 연구)

  • 김광래;유봉환
    • Journal of the Korean Society for Precision Engineering
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    • v.14 no.4
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    • pp.30-37
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    • 1997
  • This thesis is concerned with the study on the characteristics of the tool failure occuring at the beginning of cutting in finish machining of hardened steels such as carbon tool steel and alloy tool steel by a ceramic tool (Al$_{2}$O$_{3}$+TiC) with nose radius. In the machining of hardened carbon steel STC3, the wear mechanism on the flank face of the ceramic tool is abrasion wear. The mode of tool failure is developed into catastropic fracture with flaking. It is thought that the fracture caused by FeO and TiO$_{2}$ results from the oxidation of Fe in the workpice and TiC in the ceramic tool and the deposit of Fe formed on the surface of the ceramic tool. In the machining of hardened alloy steel STD11, the wear mechanism on the flank face of the ceramic tool is that abrasion and adhesion wear exist simultaneously. The mode of tool failure at the beginning of cutting features is DOC notch wear. It is thought that the DOC notch wear caused by FeO and TiO$_{2}$results from the oxidation of Fe and TiC in the workpiece and ceramic tool, respectively.

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Erosion Behavior of SiC Coated C/C Composites with Condition of Combustion Test

  • Joo, Hyeok-Jong;Min, Kyung-Dae;Lee, Jae-Won
    • Carbon letters
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    • v.4 no.3
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    • pp.133-139
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    • 2003
  • Carbon/carbon composites are ideal candidates for a number of aerospace applications including structural materials for advanced vehicles, leading edges, structures of re-entry and hypersonic vehicles and propulsion systems. One serious defect for such application of the carbon/carbon composites is their poor oxidation resistance in high temperature oxidizing environments. SiC coating was employed to protect the composites from oxidation. It is mechanically and chemically stable under extreme thermal and oxidative environments, provides good adhesion to the substrate, and offers good thermal shock resistance. The SiC layer on the nozzle machined from the carbon/carbon composites was formed by pack-cementation method. Then, erosion characteristic of SiC coated carbon/carbon nozzle was examined by combustion test using a liquid rocket motor. The erosion rates were measured as function of combustion pressure, ratio of oxygen to fuel, combustion time, density of the composites and geometry of reinforced carbon fibre in the composites. The morphology change of the composites after combustion test was investigated using SEM and erosion mechanism also was discussed.

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NO Emission Characteristics of Oxygen-Enriched Combustion with $CO_2$ Recirculation in Counterflow Diffusion Flame (대향류 화염에서 $CO_2$ 재순환 산소부화연소의 NO 배출 특성)

  • Park, June-Sung;Cho, Han-Chang;Park, Jeong
    • Journal of the Korean Society of Combustion
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    • v.12 no.1
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    • pp.28-37
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    • 2007
  • Numerical study is conducted to grasp the flame structure and NO emissions for a wide range of oxy-fuel combustion (covering from air blown combustion to pure oxygen combustion) and for various mole fractions of recirculated $CO_2$ in $CH4-O_2/N_2/CO_2$ counterflow diffusion flames. Special concern is given to the difference of the flame structure and NO emissions between air blown combustion and oxy-fuel combustion w/o recirculated $CO_2$ and is also focused on chemical effects of recirculated $CO_2$. Air blown combustion and oxy-fuel combustion w/o recirculated $CO_2$ are shown to be considerably different in the flame structure and NO emissions. Modified fuel oxidation reaction pathways in oxygen-enriched combustion are provided in detail compared to those in air blown combustion w/o recirculated $CO_2$. The formation and destruction of NO through Fenimore and thermal mechanisms are also compared for air blown combustion and oxyegn-enriched combustion w/o recirculated $CO_2$, and the role of the recirculated $CO_2$ and its chemical effects are discussed. Importantly contributing reaction steps to the formation and destruction of NO are also estimated in oxygen-enriched combustion in comparison to air blown combustion.

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Leaching Mechanism and Modelling of U$O_2$ Pellets (U$O_2$ Pellet의 침출거동 및 Modelling)

  • Chang, Kil-Sang;Chun, Kwan-Sik;Park, Hyun-Soo;Suh, In-Suk
    • Nuclear Engineering and Technology
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    • v.20 no.3
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    • pp.155-164
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    • 1988
  • A rate equation for UO$_2$ pellet leaching has been derived and compared with some experimental results. The leach rate model comprises the processes of oxygen penetration into UO$_2$ pellets and the dissolution and transport of oxidized UO$_2$ depending on the penetration depth of oxygen. The model may be analyzed with two regions of transient and steady state behaviors, which should depend on the initial oxidation state of pellets. Also this model can be utilized in the analyses of general leach processes if the oxidation reaction of UO$_2$ is replaced with similar mechanism of those processes.

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Synergistic Effects of Mo-V Based Mixed Oxide Catalysts for Acrolein Oxidation(I) (아크로레인 산화용 Mo-V 계 혼합산화물 촉매의 상승효과(I))

  • Na, Suk-Eun;Kim, Kyung-Hoon;Chung, Jong-Shik;Park, Dae-Won
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.717-721
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    • 1992
  • Mechanical mixtures of vanadium molybdate and copper molybdate catalysts prepared by coprecipitation method, and those of $MoO_3$ and $V_2O_5$ were used to study the synergistic effects between each metal oxide for the selective oxidation of acrolein. The catalytic activity results revealed that the conversion of acrolein and yield of acrylic acid were increased with the mixture catalysts and it could be explained by a remote control mechanism. Thermal gravimetric analysis confirmed the evolution of lattice oxygen in the mixture catalysts.

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Characteristics of Electricity Production by Metallic and Non-metallic Anodes Immersed in Mud Sediment Using Sediment Microbial Fuel Cell

  • Haque, Niamul;Cho, Dae-Chul;Kwon, Sung-Hyun
    • Journal of Environmental Science International
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    • v.23 no.10
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    • pp.1745-1753
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    • 2014
  • Sediment microbial fuel cell (SMFC), equipped with Zn, Al, Cu, Fe or graphite felt (GF) anode and marine sediment, was performed. Graphite felt was used as a common cathode. SMFC was single chambered and did not use any redox mediator. The aim of this work was to find efficient anodic material. Oxidation reduction potential (ORP), cell voltage, current density, power density, pH and chemical oxygen demand (COD) were measured for SMFC's performance.. The order of maximum power density was $913mWm^{-2}$ for Zn, $646mWm^{-2}$ for Fe, $387.8mWm^{-2}$ for Cu, $266mWm^{-2}$ for Al, and $127mWm^{-2}$ for graphite felt (GF). The current density over voltage was found to be strongly correlated with metal electrodes, but the graphite felt electrode, in which relatively weaker electricity was observed because of its bio-oriented mechanism. Metal corrosion reactions and/or a complicated microbial electron transfer mechanism acting around the anodic compartment may facilitate to generate electricity. We presume that more sophisticated selection of anodic material can lead to better performance in SMFC.

Potential Energy Surfaces for the Reaction Al + O2→ AlO + O

  • Ledentu, Vincent;Rahmouni, Ali;Jeung, Gwang-Hi;Lee, Yoon-Sup
    • Bulletin of the Korean Chemical Society
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    • v.25 no.11
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    • pp.1645-1647
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    • 2004
  • Potential energy surfaces for the reaction Al + $O_2{\to}$AlO + O have been calculated with the multireference configuration interaction (MRCI) method using molecular orbitals derived from the complete active space selfconsistent field (CASSCF) calculations. The end-on geometry is the most favourable for the reaction to take place. The small reaction barrier in the present calculation (0.11 eV) is probably an artefact related to the ionicneutral avoided crossing. The charge analysis implies that the title oxidation reaction occurs through a harpooning mechanism. Along the potential energy surface of the reaction, there are two stable intermediates of $AlO_2(C_{{\infty}v}$ and $C_{2v}$) at least 2.74 eV below the energy of reactants. The calculated enthalpy of the reaction (-0.07 eV) is in excellent agreement with the experimental value (-0.155 eV) in part due to the fortuitous cancellation of errors in AlO and $O_2$ calculations.

Crystal Structure of Cytochrome cL from the Aquatic Methylotrophic Bacterium Methylophaga aminisulfidivorans MPT

  • Ghosh, Suparna;Dhanasingh, Immanuel;Ryu, Jaewon;Kim, Si Wouk;Lee, Sung Haeng
    • Journal of Microbiology and Biotechnology
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    • v.30 no.8
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    • pp.1261-1271
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    • 2020
  • Cytochrome cL (CytcL) is an essential protein in the process of methanol oxidation in methylotrophs. It receives an electron from the pyrroloquinoline quinone (PQQ) cofactor of methanol dehydrogenase (MDH) to produce formaldehyde. The direct electron transfer mechanism between CytcL and MDH remains unknown due to the lack of structural information. To help gain a better understanding of the mechanism, we determined the first crystal structure of heme c containing CytcL from the aquatic methylotrophic bacterium Methylophaga aminisulfidivorans MPT at 2.13 Å resolution. The crystal structure of Ma-CytcL revealed its unique features compared to those of the terrestrial homologues. Apart from Fe in heme, three additional metal ion binding sites for Na+, Ca+, and Fe2+ were found, wherein the ions mostly formed coordination bonds with the amino acid residues on the loop (G93-Y111) that interacts with heme. Therefore, these ions seemed to enhance the stability of heme insertion by increasing the loop's steadiness. The basic N-terminal end, together with helix α4 and loop (G126 to Y136), contributed positive charge to the region. In contrast, the acidic C-terminal end provided a negatively charged surface, yielding several electrostatic contact points with partner proteins for electron transfer. These exceptional features of Ma-CytcL, along with the structural information of MDH, led us to hypothesize the need for an adapter protein bridging MDH to CytcL within appropriate proximity for electron transfer. With this knowledge in mind, the methanol oxidation complex reconstitution in vitro could be utilized to produce metabolic intermediates at the industry level.