• Title/Summary/Keyword: electrochemical interaction

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Studies on the Interaction of Alkyl Thiophosphinate with Precious Metals

  • 김동수
    • Bulletin of the Korean Chemical Society
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    • v.16 no.4
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    • pp.321-325
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    • 1995
  • Adsorption mechanisms of diisobutyl dithiophosphinate (DIBDTPI) and diisobutyl monothiophosphinate (DIBMTPI) on gold and gold-silver alloys (80:20 and 50:50) have been studied. The adsorption mechanisms on gold-silver alloys can be explained by the EC mechanism involving an electron transfer step and a chemical reaction step. Thus, the adsorption should be controlled by the E of the electrochemical oxidation of the electrode involved and the pK of the metal collector complex. Both di- and mono- thiophosphinate adsorb on 50:50 Au-Ag alloy at lower potential than on 80:20 Au-Ag alloy surface. There are no significant differences between the reactivities of DIBDTPI and DIBMTPI with precious metals except that the dithio- compound can be oxidized to dimer on gold at high potentials, while the monothio- homologue cannot. In this regard, DIBDTPI may be a better surface active reagent for pure gold than DIBMTPI.

Corrosion Characteristics of Aluminum Die Casting Alloys with Different Scrap Charge Rate (스크랩 장입 비율에 따른 다이캐스팅용 알루미늄 합금의 부식 특성)

  • Kim, Jun-Ho;Lee, Seung-Hyo
    • Journal of Surface Science and Engineering
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    • v.53 no.6
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    • pp.322-329
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    • 2020
  • The utilization of aluminum scrap is a subject of great importance in terms of reducing energy consumption and environmental protection. However, aluminum scrap contains impurities, which can degrade the properties of aluminum alloy, especially corrosion resistance. This study examines the effect of scrap charge rate of aluminum alloys about microstructures and corrosion characteristics. According to the metallographic examinations, Mg2Si tended to become coarser and its uniformity was decreased by increasing aluminum scrap charge rate. The immersion test exhibited corrosion progressed through the eutectic areas due to micro-galvanic interactions. Electrochemical measurements revealed that excess aluminum scrap could reduce the intergranular corrosion resistance of aluminum alloys. Results showed that the scrap charge rate is important factor in the design of corrosion resistance of aluminum die casting alloys.

Science High School Students' Understandings on Chemical Cells : In Relation to Chemical Equilibrium from the Microscopic Viewpoint at Molecular Level (과학고등학교 학생의 화학 전지에 대한 이해 분석: 분자적 수준의 미시적 관점에서 화학 평형과 연계하여)

  • Kim, Hyun-Jung;Hong, Hun-Gi
    • Journal of the Korean Chemical Society
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    • v.56 no.6
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    • pp.731-738
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    • 2012
  • The purpose of this study is to analyze the understandings of science high school students on the conception of chemical cell in relation to chemical equilibrium from the microscopic viewpoint at molecular level through questionnaires and follow-up interviews. The results show that they have high understandings on the chemical equilibrium states in the electrochemical cell and on the redox reaction taking place simultaneously when a metal electrode is immersed in the metal ion solution. However, they do not fully comprehend the development of electrical potential difference, electron movement, electrode potential measurement in the half-cells, and calculation of the net cell voltage between anode and cathode in the chemical cell because of difficulties in the microscopic understanding the interaction on the interface at the electrode and the electrolyte solution.

Structural, Electrochemical, DNA Binding and Cleavage Properties of Nickel(II) Complex [Ni(H2biim)2(H2O)2]2+ of 2,2'-Biimidazole

  • Jayamani, Arumugam;Thamilarasan, Vijayan;Ganesan, Venketasan;Sengottuvelan, Nallathambi
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3695-3702
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    • 2013
  • A nickel(II) complex $[Ni(H_2biim)_2(H_2O)_2](ClO_4)_2{\cdot}H_2O$ (1) of biimidazole ligand has been synthesized and characterized (Where $H_2biim$ = 2,2'-biimidazole). The single crystal X-ray diffraction of the complex shows a dimeric structure with six coordinated psudo-octahedral geometry. The cyclic voltammograms of complex exhibited one quasireversible reduction wave ($E_{pc}=-0.61V$) and an irreversible oxidation wave ($E_{pa}=1.28V$) in DMF solution. The interaction of the complex with Calf-Thymus DNA (CT-DNA) has been investigated by absorption and fluorescence spectroscopy. The complex is an avid DNA binder with a binding constant value of $1.03{\times}10^5M^{-1}$. The results suggest that the nickel(II) complex bind to CT-DNA via intercalative mode and can quench the fluorescence intensity of EB bind to CT-DNA with $K_{app}$ value of $3.2{\times}10^5M^{-1}$. The complex also shown efficient oxidative cleavage of supercoiled pBR322 DNA in the presence of hydrogen peroxide as oxidizing agent. The DNA cleavage by complex in presence of quenchers; viz. DMSO, KI, $NaN_3$ and EDTA reveals that hydroxyl radical or singlet oxygen mechanism is involved. The complex showed invitro antimicrobial activity against four bacteria and two fungi. The antimicrobial activity was nearer to that of standard drugs and greater than that of the free ligand.

Preparation of Solid Polymer Electrolytes of PSf-co-PPSS/Heterooolyacid [HPA] Composite Membrane for Hydrogen Production via Water Elecrolysis (PSf-co-PPSS/HPA를 이용한 수소제조 수전해용 고체 고분자 전해질 복합 막의 제조)

  • Jung, Yun-Kyo;Lee, Hyuck-Jae;Jang, In-Young;Hwang, Gab-Jin;Bae, Ki-Kwang;Sim, Kyu-Sung;Kang, An-Soo
    • Journal of Hydrogen and New Energy
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    • v.16 no.2
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    • pp.103-110
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    • 2005
  • Proton conducting solid polymer electrolyte (SPE) membranes have been used in many energy technological applications such as water electolysis, fuel cells, redox-flow battery, and other electrochemical devices. The availability of stable membranes with good electrochemical characteristics as proton conductivity at high temperatures above 80 $^{\circ}C$ and low cost are very important for its applications. However, the presently available perfluorinated ionomers are not applicable because of high manufacturing cost and high temperature use to the decrease in the proton conductivity and mechanical strength. In order to make up for the weak points, the block copolymer (BPSf) of polysulfone and poly (phenylene sulfide sulfone) were synthesized and sulfonated. The electrolyte membranes were prepared with phosphotungstic acid (HPA)/sulfonated BPSf via solution blending. This study would be desirable to investigate the interaction between the HPA and sulfonated polysulfone. The results showed that the characteristics of SPSf/HPA blend membrane was a better than Nafion at high temperature, 100 $^{\circ}C$. These membranes proved to have a high proton conductivity, $6.29{\times}10-2$ S/cm, a water content, 23.9%, and a ion exchange capacity, 1.97 meq./g dry membrane. Moreover, some of the membranes kept their high thermal and mechanical stability.

Structural Analysis of Species in NbCI5-EMIC Room-Temperature Molten Salt with Raman Spectroscopic Measurement and Ab Initio Molecular Orbital Calculation

  • Koura, Nobuyuki;Matsuzawa, Hidenori;Kato, Tomoki;Idemoto, Yasushi;Matsumoto, Futoshi
    • Journal of the Korean Electrochemical Society
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    • v.5 no.4
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    • pp.183-188
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    • 2002
  • The structure of species formed in $NbCI_5-I-ethyl-3-methylimidazolium$ chloride (EMIC) room-temperature molten salt (RTMS) was examined with the Raman spectroscopic measurement and ab initio molecular orbital calculation. The equilibrium structures of $NbCl_5,\;NbCl_6^-,\;Nb_2CI_{10},\;Nb_2CI_{11}^-,\;Nb_3CI_6^-,\;NbCI_6^--EMI^+\;(in\;which\;NbCI_6^-$ anion approaches $EMI^+$ cation with strong interaction) and $Nb_2CI_{11}^--EMI^+$ were obtained with the HF/LANL2DZ level of calculation. The harmonic frequencies at each equilibrium structure were compared with Raman spectra. The harmonic frequencies of $NbCI_6^--EMI^+,\; Nb_2CI_{11}^--EMI^+,\;and\;Nb_2CI_{10}$ were in good agreement with the Raman spectra of RTMS melts. In the $NbCI_5-EMIC RTMS$, the main species were $NbCI_6^-\;and\;EMI^+$. In the $NbCl_5-EMIC$ RTMS added $NbCl_5\;over\;50mol\%$, small amount of $Nb_2CI_{11}^-\;and\; Nb_2CI_{10}$ were also formed. The structures of anions and cation in the RTMS distorted from free ions with Coulomb force.

1,n-Alkanedithiol (n = 2, 4, 6, 8, 10) Self-Assembled Monolayers on Au(111): Electrochemical and Theoretical Approach

  • Qu, Deyu;Kim, Byung-Cheol;Lee, Chi-Woo J.;Uosaki, Kohei
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2549-2554
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    • 2009
  • The structures of 1,n-alkanedithiol (n = 2, 4, 6, 8, 10) self-assembled monolayers (SAMs) on a Au(111) substrate were investigated by electrochemical measurements and theoretical calculations. The results of the experimental techniques indicated that the dithiols, except n = 2, showed an upright molecular structure in the SAMs, in which alkanedithiols were bound to the Au surface via only one thiol functionality and the other one faced up to the air. The results also suggested that the formed dithiol SAMs were densely packed and highly oriented. Except ethanedithiol, which was thought to form a bilayer, the reductive desorption peak potentials of 1,n-alkanedithiol (n = 4, 6, 8, 10) SAMs were more negative than those of the corresponding monothiol ones in 0.1 M KOH solutions. This illustrates that the dithiol SAMs had higher stability than the corresponding monothiol ones. The major part of the high stability may be attributed to the van der Waals interaction among the sulfur atoms on top of the dithiol SAMs. The molecular modeling calculation showed that the structures of dithiol SAMs were similar to those of the corresponding monothiol SAMs and that all the dithiol SAMs, except ethanedithiol, were more stable than the corresponding monothiol SAMs. The calculated energy differences between dithiol and monothiol SAMs decreased with the increment of alkyl-chain length.

Electrochemical Behavior of Sm(III) on the Aluminium-Gallium Alloy Electrode in LiCl-KCl Eutectic

  • Ye, Chang-Mei;Jiang, Shi-Lin;Liu, Ya-Lan;Xu, Kai;Yang, Shao-Hua;Chang, Ke-Ke;Ren, Hao;Chai, Zhi-Fang;Shi, Wei-Qun
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.19 no.2
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    • pp.161-176
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    • 2021
  • In this study, the electrochemical behavior of Sm on the binary liquid Al-Ga cathode in the LiCl-KCl molten salt system is investigated. First, the co-reduction process of Sm(III)-Al(III), Sm(III)-Ga(III), and Sm(III)-Ga(III)-Al(III) on the W electrode (inert) were studied using cyclic voltammetry (CV), square-wave voltammetry (SWV) and open circuit potential (OCP) methods, respectively. It was identified that Sm(III) can be co-reduced with Al(III) or Ga(III) to form AlzSmy or GaxSmy intermetallic compounds. Subsequently, the under-potential deposition of Sm(III) at the Al, Ga, and Al-Ga active cathode was performed to confirm the formation of Sm-based intermetallic compounds. The X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analyses indicated that Ga3Sm and Ga6Sm intermetallic compounds were formed on the Mo grid electrode (inert) during the potentiostatic electrolysis in LiCl-KCl-SmCl3-AlCl3-GaCl3 melt, while only Ga6Sm intermetallic compound was generated on the Al-Ga alloy electrode during the galvanostatic electrolysis in LiCl-KCl-SmCl3 melt. The electrolysis results revealed that the interaction between Sm and Ga was predominant in the Al-Ga alloy electrode, with Al only acting as an additive to lower the melting point.

Hydroxide ion Conduction Mechanism in Mg-Al CO32- Layered Double Hydroxide

  • Kubo, Daiju;Tadanaga, Kiyoharu;Hayashi, Akitoshi;Tatsumisago, Masahiro
    • Journal of Electrochemical Science and Technology
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    • v.12 no.2
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    • pp.230-236
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    • 2021
  • Ionic conduction mechanism of Mg-Al layered double hydroxides (LDHs) intercalated with CO32- (Mg-Al CO32- LDH) was studied. The electromotive force for the water vapor concentration cell using Mg-Al CO32- LDH as electrolyte showed water vapor partial pressure dependence and obeyed the Nernst equation, indicating that the hydroxide ion transport number of Mg-Al CO32- LDH is almost unity. The ionic conductivity of Mg(OH)2, MgCO3 and Al2(CO3)3 was also examined. Only Al2(CO3)3 showed high hydroxide ion conductivity of the order of 10-4 S cm-1 under 80% relative humidity, suggesting that Al2(CO3)3 is an ion conducting material and related to the generation of carrier by interaction with water. To discuss the ionic conduction mechanism, Mg-Al CO32- LDH having deuterium water as interlayer water (Mg-Al CO32- LDH(D2O)) was prepared. After the adsorbed water molecules on the surface of Mg-Al CO32- LDH(D2O) were removed by drying, DC polarization test for dried Mg-Al CO32- LDH(D2O) was examined. The absorbance attributed to O-D-stretching band for Mg-Al CO32- LDH(D2O) powder at around the positively charged electrode is larger than that before polarization, indicating that the interlayer in Mg-Al CO32- LDH is a hydroxide ion conduction channel.

Synergistically Enhanced Oxygen Evolution Catalysis with Surface Modified Halloysite Nanotube

  • Hyeongwon Jeong;Bharat Sharma;Jae-ha Myung
    • Journal of Electrochemical Science and Technology
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    • v.14 no.1
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    • pp.96-104
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    • 2023
  • Synergistically increased oxygen evolution reaction (OER) of manganese oxide (MnO2) catalyst is introduced with surface-modified halloysite nanotube (Fe3O4-HNTs) structure. The flake shaped MnO2 catalyst is attached on the nanotube template (Fe3O4-HNTs) by series of wet chemical and hydrothermal method. The strong interaction between MnO2 and Fe3O4-HNTs maximized active surface area and inter-connectivity for festinate charge transfer reaction for OER. The synergistical effect between Fe3O4 layer and MnO2 catalyst enhance the Mn3+/Mn4+ ratio by partial replacement of Mn ions with Fe. The relatively increased Mn3+/Mn4+ ratio on MnO2@FHNTs induced 𝜎* orbital (eg) occupation close to single electron, improving the OER performances. The MnO2@FHNTs catalyst exhibited the reduced overpotential of 0.42 V (E vs. RHE) at 10 mA/cm2 and Tafel slope of (99 mV/dec), compared with that of MnO2 with unmodified HNTs (0.65 V, 219 mV/dec) and pristine MnO2 (0.53 V, 205 mV/dec). The present study provides simple and innovative method to fabricate nano fiberized OER catalyst for a broad application of energy conversion and storage systems.