• Title/Summary/Keyword: proton reaction

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Autoxidation Core@Anti-Oxidation Shell Structure as a Catalyst Support for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cell

  • Heo, Yong-Kang;Lee, Seung-Hyo
    • Corrosion Science and Technology
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    • v.21 no.5
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    • pp.412-417
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    • 2022
  • Proton exchange membrane fuel cells (PEMFCs) provide zero emission power sources for electric vehicles and portable electronic devices. Although significant progresses for the widespread application of electrochemical energy technology have been achieved, some drawbacks such as catalytic activity, durability, and high cost of catalysts still remain. Pt-based catalysts are regarded as the most efficient catalysts for sluggish kinetics of oxygen reduction reaction (ORR). However, their prohibitive cost limits the commercialization of PEMFCs. Therefore, we proposed a NiCo@Au core shell structure as Pt-free ORR electrocatalyst in PEMFCs. NiCo alloy was synthesized as core to introduce ionization tendency and autoxidation reaction. Au as a shell was synthesized to prevent oxidation of core NiCo and increase catalytic activity for ORR. Herein, we report the synthesis, characterization, electrochemical properties, and PEMFCs performance of the novel NiCo@Au core-shell as a catalyst for ORR in PEMFCs application. Based on results of this study, possible mechanism for catalytic of autoxidation core@anti-oxidation shell in PEMFCs is suggested.

Quantum Mechanical Studies for Proton Transfer in HOCl + HCl and H2O + ClONO2 on Water Clusters

  • Kim, Yong-Ho;Park, Chea-Yong;Kim, Kyung-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.26 no.12
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    • pp.1953-1961
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    • 2005
  • We have performed high-level quantum mechanical calculation for multiple proton transfer in HOCl + HCl and $H_2O$ + $ClONO_2$ on water clusters, which can be used as a model of the reactions on ice surface in stratospheric clouds. Multiple proton transfer on ice surface plays crucial role in these reactions. The structures of the clusters with 0-3 water molecules and the transition state structures for the multiple proton transfer have been calculated. The energies and barrier heights of the proton transfer were calculated at various levels of theory including multi-coefficient correlated quantum mechanical methods (MCCM) that have recently been developed. The transition state structures and the predicted reaction mechanism depend very much on the level of theory. In particular, the HF level can not correctly predict the TS structure and barrier heights, so the electron correlation should be considered appropriately.

Excess proton catalyzed H/D exchange reaction at the ice surface

  • Moon, Eui-Seong;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.333-333
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    • 2011
  • We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.

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An Amperometric Proton Selective Sensor with an Elliptic Microhole Liquid/Gel Interface for Vitamin-C Quantification

  • Faisal, Shaikh Nayeem;Hossain, Md. Mokarrom;Lee, Hye-Jin
    • Journal of Electrochemical Science and Technology
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    • v.1 no.2
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    • pp.121-126
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    • 2010
  • An amperometric ascorbic acid selective sensor utilizing the transfer reaction of proton liberated from the dissociation of ascorbic acid in aqueous solution across an elliptic micro-hole water/organic gel interface is demonstrated. This redox inactive sensing platform offers an alternative way for the detection of ascorbic acid to avoid a fouling effect which is one of the major concerns in redox based sensing systems. The detection principle is simply measuring the current change with respect to the assisted transfer of protons by a proton selective ionophore (e.g., ETH 1778) across the micro-hole interface between the water and the polyvinylchloride-2-nitrophenyloctylether gel phase. The assisted transfer reaction of protons generated from ascorbic acid across the polarized micro-hole interface was first characterized using cyclic voltammetry. An improved sensitivity for the quantitative analysis of ascorbic acid was achieved using differential pulse stripping voltammetry with a linear response ranging from 1 to $100\;{\mu}M$ concentrations of ascorbic acid. As a demonstration, the developed sensor was applied for analyzing the content of vitamin-C in different types of commercial pharmaceutical tablets and syrups, and a satisfactory recovery from these samples were also obtained.

Preparation and Characterization of Proton Conducting Membranes by Blending PVC-g-PHEA and PVA

  • Koh, Jong-Kwan;Choi, Jin-Kyu;Seo, Jin-Ah;Zeng, Xiaolei;Kim, Jong-Hak
    • Korean Membrane Journal
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    • v.11 no.1
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    • pp.1-7
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    • 2009
  • This work reports the preparation of proton conductive crosslinked polymer electrolyte membranes by blending poly(vinyl chloride)-g-poly(hydroxyl ethyl acrylate) (PVC-g-PHEA) and poly(vinyl alcohol) (PVA). The PHEA chains of the graft copolymer were crosslinked with PVA using sulfosuccinic acid (SA) via the esterification reaction between -OH of polymer matrix and -COOH of SA. The PVC-g-PHEA graft copolymer was synthesized via atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC backbones. Ion exchange capacity (IEC) continuously increased with increasing concentrations of SA, due to the increasing portion of charged groups in the membrane. However, the water uptake increased up to 20.0 wt% of SA concentration above which it decreased monotonically. The membrane exhibited a maximum proton conductivity of 0.026 S/cm at 20.0 wt% of SA concentration, which is presumably due to competitive effect between the increase of ionic sites and the crosslinking reaction.

A Study on Measurement of Gamma-ray Spectrum for the Natural Tungsten nuclear reaction by using KOMAC proton Linear Accelerator (KOMAC 양성자 선형가속기를 이용한 천연 텅스텐 핵반응에 대한 감마선 스펙트럼 측정에 대한 연구)

  • Lee, Samyol
    • Journal of the Korean Society of Radiology
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    • v.12 no.2
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    • pp.133-138
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    • 2018
  • The measurement of gamma-ray spectrum of $^{nat}W(p,xn)$ reaction with natural tungsten were performed by using a high energy proton generated from a 100-MeV proton linear accelerator of the Korea Multi-purpose Accelerator Complex (KOMAC). Gamma rays generated by various nuclides generated through the nuclide were measured using a gamma-ray spectroscopy system composed of HPGe detector. A gamma-ray standard source was used for energy calibration and efficiency measurement of the detector. Analysis of the gamma rays observed in the measured spectra showed that the radionuclides produced were $^{167}Re$, $^{178}Re$, $^{179}Re$, $^{180}Re$, $^{181}Re$, $^{182}Re$, $^{184}Re$, $^{172}Ta$, $^{174}Ta$, $^{178}Ta$, $^{182}Ta$, $^{184}Ta$, $^{175}W$, $^{176}W$, $^{177}W$ and $^{179}W$. Nuclides were generated. The results of this study will be applied to nuclear fusion, astrophysics, and nuclear medicine applications in the future.

Phosphoric Acid-doped SDF-F/poly(VI-co-MPS)/PTFE Membrane for a High Temperature Proton Exchange Membrane Fuel Cell

  • Lee, Jong-Won;Yi, Cheol-Woo;Kim, Keon
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1902-1906
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    • 2011
  • Sulfonated poly(fluorinated arylene ether)s (SDF-F)/poly[(N-vinylimidazole)-co-(3-methacryloxypropyl-trimethoxysilane)] (poly(VI-co-MPS))/poly(tetrafluoroethylene) (PTFE) is prepared for a high temperature proton exchange membrane fuel cell (PEMFC). The reaction of the membrane with phosphoric acid forms silicate phosphor, as a chemically bound proton carrier, in the membrane. Thus-formed silicate phosphor, nitrogen in the imidazole ring, and physically bound phosphoric acid act as proton carriers in the membrane. The physico-chemical and electrochemical properties of the membrane are investigated by various analytical tools. The phosphoric acid uptake and proton conductivity of the SDF-F/poly(VI-co-MPS)/PTFE membrane are higher than those of SDF-F/PVI/PTFE. The power densities of cells with SDF-F/poly(VI-co-MPS)/PTFE membranes at 0.6 V are 286, 302, and 320 mW $cm^{-2}$ at 150, 170, and 190 $^{\circ}C$, respectively. Overall, the SDFF/poly(VI-co-MPS)/PTFE membrane is one of the candidates for anhydrous HT-PEMFCs with enhanced mechanical strength and improved cell performance.

Synthesis and Characterization of Sulfonated Poly(arylene ether) Polyimide Multiblock Copolymers for Proton Exchange Membranes

  • Lee, Hae-Seung;Roy Abhishek;Badami Anand S.;McGrath James E.
    • Macromolecular Research
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    • v.15 no.2
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    • pp.160-166
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    • 2007
  • Novel multiblock copolymers, based on segmented sulfonated hydrophilic-hydrophobic blocks, were synthesized and investigated for their application as proton exchange membranes. A series of segmented sulfonated poly(arylene ether sulfone)-b-polyimide multiblock copolymers, with various block lengths, were synthesized via the coupling reaction between the terminal amine moieties on the hydrophilic blocks and naphthalene anhydride functionalized hydrophobic blocks. Successful imidization reactions required a mixed solvent system, comprised of NMP and m-cresol, in the presence of catalysts. Proton conductivity measurements revealed that the proton conductivity improved with increasing hydrophilic and hydrophobic block lengths. The morphological structure of the multiblock copolymers was investigated using tapping mode atomic force microscopy (TM-AFM). The AFM images of the copolymers demonstrated well-defined nanophase separated morphologies, with the changes in the block length having a pronounced effect on the phase separated morphologies of the system. The self diffusion coefficient of water, as measured by $^1H$ NMR, provided a better understanding of the transport process. Thus, the block copolymers showed higher values than Nafion, and comparable proton conductivities in liquid water, as well as under partially hydrated conditions at $80^{\circ}C$. The new materials are strong candidates for use in PEM systems.