• Title/Summary/Keyword: electrochemical reduction

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Synthesis and Electrochemical Characteristics of Rare Earths Metal Complexes (희토류금속 착물의 합성과 전기화학적 특성)

  • Chil Nam Choe;Suk Jin Yuon;Il Du Kim;Sung Pyung Kim;Youn Soo Sohn
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.496-503
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    • 1989
  • The chemical behavior of trivalent lanthanide (Pr(III) and Yb(III)) and 2, 2, 6, 6-tetramethyl-3, 5-heptanedione(dipivaloylmethane) complexes was investigated by the use of direct current, differential pulse polarography and cyclic voltammetry. In this study, it was founded that the reduction of trivalent lanthanide complexes was observed by one electron transfer process at Epc = -0. 13 V and -0.80 V of Pr(III), and -0.02 V of Yb(III) vs. Ag-AgCl electrode. Also, it was founded that the treatment of DP and CV to the case of a first-order chemical equilibrium reaction preceding a reversible and irreversible one electron transfer reaction, (a >0. 5) the socalled ErCr electrode process. The equilibrium constant (lnK) obtained, of various solvents, these constant were founded to be increases with decreasing dielectric constant of the solvents. Plots of lnK for these reaction against ln(l/D) for the solvents was fairly straight lines, and the behavior of the heavier lanthanides was decreased equilibrium constant with increasing atomic number.

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Atmospheric Effects on Growth Kinetics and Electronic Properties of Passive Film of Aluminum in Borate Buffer Solution (Borate 완충용액에서 알루미늄의 산화피막의 생성과정과 전기적 성질에 대한 대기의 영향)

  • Kim, Younkyoo
    • Journal of the Korean Chemical Society
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    • v.60 no.3
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    • pp.169-176
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    • 2016
  • In a borate buffer solution, the growth kinetics and the electronic properties of passive film on aluminum were investigated, using the potentiodynamic method, chronoamperometry, and multi-frequency electrochemical impedance spectroscopy. The corrosion of aluminum was heavily influenced by the degree of oxygen concentration because of the increasing reduction current. The oxide film formed during the passivation process of aluminum has showed the electronic properties of n-type semiconductor, which follow from the Mott-Schottky equation. It was found out that the passive film (Al(OH)3) of Al formed in the low electrode potential changes to Al2O3 while the electrode potential increases. The growth kinetics data as measured by chronoamperometry suggests a mechanism in which the growth of the film of Al2O3 is determined by field-assisted transport of ions through the film.

A Zinc Porphyrin Sensitizer Modified with Donor and Acceptor Groups for Dye-Sensitized Solar Cells

  • Lee, Seewoo;Sarker, Ashis K.;Hong, Jong-Dal
    • Bulletin of the Korean Chemical Society
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    • v.35 no.10
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    • pp.3052-3058
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    • 2014
  • In this article, we have designed and synthesized a novel donor-${\pi}$-acceptor (D-${\pi}$-A) type porphyrin-based sensitizer (denoted UI-5), in which a carboxyl anchoring group and a 9,9-dimethyl fluorene were introduced at the meso-positions of porphyrin ring via phenylethynyl and ethynyl bridging units, respectively. Long alkoxy chains in ortho-positions of the phenyls were supposed to reduce the degree of dye aggregation, which tends to affect electron injection yield in a photovoltaic cell. The cyclic voltammetry was employed to determine the band gap of UI-5 to be 1.41 eV based on the HOMO and LUMO energy levels, which were estimated by the onset oxidation and reduction potentials. The incident monochromatic photon-to-current conversion efficiency of the UI-5 DSSC assembled with double-layer (20 nm-sized $TiO_2$/400 nm-sized $TiO_2$) film electrodes appeared lower upon overall ranges of the excitation wavelengths, but exhibited a higher value over the NIR ranges (${\lambda}$ = 650-700 nm) compared to the common reference sensitizer N719. The UI-5-sensitized cell yielded a relatively poor device performance with an overall conversion efficiency of 0.74% with a short circuit photocurrent density of $3.05mA/cm^2$, an open circuit voltage of 0.54 mV and a fill factor of 0.44 under the standard global air mass (AM 1.5) solar conditions. However, our report about the synthesis and the photovoltaic characteristics of a porphyrin-based sensitizer in a D-${\pi}$-A structure demonstrated a significant complex relationship between the sensitizer structure and the cell performance.

Newly Developed BioDegradable Mg Alloys and Its Biomedical Applications

  • Seok, Hyeon-Gwang;Kim, Yu-Chan;Yang, Gui Fu;Cha, Pil-Ryeong;Jo, Seong-Yun;Yang, Seok-Jo
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.55.2-55.2
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    • 2012
  • Intensive theoretical and experimental studies have been carried out at Korean Institute of Science and Technology (KIST) on controlling the bio absorbing rate of the Mg alloys with high mechanical strength through tailoring of electrochemical potential. Key technology for retarding the corrosion of the Mg alloys is to equalize the corrosion potentials of the constituent phases in the alloys, which prevented the formation of Galvanic circuit between the constituent phases resulting in remarkable reduction of corrosion rate. By thermodynamic consideration, the possible phases of a given alloy system were identified and their work functions, which are related to their corrosion potentials, were calculated by the first principle calculation. The designed alloys, of which the constituent phases have similar work function, were fabricated by clean melting and extrusion system. The newly developed Mg alloys named as KISTUI-MG showed much lower corrosion rate as well as higher strength than previously developed Mg alloys. Biocompatibility and feasibility of the Mg alloys as orthopedic implant materials were evaluated by in vitro cell viability test, in vitro degradation test of mechanical strength during bio-corrosion, in vivo implantation and continuous observation of the implant during in vivo absorbing procedures. Moreover, the cells attached on the Mg alloys was observed using cryo-FIB (focused ion beam) system without the distortion of cell morphology and its organ through the removal of drying steps essential for the preparation of normal SEM/TEM samples. Our Mg alloys showed excellent biocompatibility satisfying the regulations required for biomedical application without evident hydrogen evolution when it implanted into the muscle, inter spine disk, as well as condyle bone of rat and well contact interface with bone tissue when it was implanted into rat condyle.

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Synthesis of Tridentate Schiff base Molybdenum(Ⅴ) Complexes and Their Electrochemical Properties in Aprotic Solvents (세자리 Schiff base 몰리브데늄(Ⅴ) 착물들의 합성과 비수용매에서의 전기화학적 성질)

  • Choi, Young-Kook;Song, Mi-Sook;Rim, Chae-Pyeong;Chjo, Ki-Hyung
    • Journal of the Korean Chemical Society
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    • v.39 no.1
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    • pp.47-56
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    • 1995
  • Tridentate Schiff base molybdenum(V) complexes such as [Mo(Ⅴ)2O(SOHB)4], [Mo(Ⅴ)2O3(SOIP)2(NCS)2] and [Mo(Ⅴ)2O3(SOTB)2(H20)2](SOHB: Salicylidene-o-imino hydroxybenzene, SOIP; Salicylidene-o-imino pyridine, SOTB; Salicylidene-o-imino thiolbenzene) were synthesized and identified by elemental analysis, spectroscopy, and thermogravimetric analysis (TGA). It was found that the mole ratio of Schiff base ligand to the metal in these complexes is 1 : 1 or 1 : 2. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic techniques in nonaquous solvent containing 0.1 M tetraethylammonium perchlorate (TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes with one electron were Mo(Ⅴ)Mo(Ⅴ)e-→ Mo(Ⅴ)Mo(Ⅳ)e-→Mo(Ⅳ)Mo(Ⅳ)e-→Mo(Ⅳ)Mo(Ⅲ).

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Electronic Structure and Electrochemistry of Complexes Trans-bis(tri-phenyl phosphine) Palladium(II) and Nickel(II) with Ligands $(CH_3COO-,\;Cl-\;and\;CO)$ (리간드 $(CH_3COO-,\;Cl-,\;CO)$와 트란스-비스(트리페닐포스핀) 팔라듐(II) 과 니켈(II) 착물들에 대한 전자적구조와 전기화학적 연구)

  • Choe Chil Nam;Jung Oh Jin;Kim Se Bong
    • Journal of the Korean Chemical Society
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    • v.36 no.1
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    • pp.44-50
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    • 1992
  • The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

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Effect of Aluminum and Silicon on Atmospheric Corrosion of Low-alloying Steel under Containing NaHSO3 Wet/dry Environment

  • Chen Xinhua;Dong Junhua;Han Enhou;Ke Wei
    • Corrosion Science and Technology
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    • v.7 no.6
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    • pp.315-318
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    • 2008
  • The atmospheric corrosion performance of Al-alloying, Si-alloying and Al-Si-alloying steel were studied by wet/dry cyclic corrosion tests (CCT) at $30^{\circ}C$ and 60% relative humidity (RH). The corrosion electrolyte used for CCT was 0.052 wt% $NaHSO_{3}$ (pH~4) solution. The result of gravimetry demonstrated that Al-Si-bearing steels showed lower corrosion resistance than other rusted steels. But the rusted 0.7%Si-alloying steel showed a better corrosion resistance than rusted mild steel. Polarization curves demonstrated that Al-/Si-alloying and Al-Si-alloying improved the rest potential of steel at the initial stage; and accelerated the cathodic reduction and anodic dissolution after a rust layer formed on the surfaces of steels. XRD results showed that Al-Si-alloying decreased the volume fraction of $Fe_{3}O_{4}$ and $\alpha-FeOOH$. The recycle of acid accelerated the corrosion of steel at the initial stage. After the rust layer formed on the steel, the leak of rust destabilized the rust layer due to the dissolution of compound containing Al (such as $FeAl_{2}O_{4}$, $(Fe,\;Si)_{2}(Fe,\;Al)O_{4}$). Al-Si-alloying is hence not suitable for improving the anti-corrosion resistance of steel in industrial atmosphere.

Highly Efficient Red Emissive Heteroleptic Cyclometalated Iridium(III) Complexes Bearing Two Substituted 2-Phenylquinoxaline and One 2-Pyrazinecarboxylic Acid

  • Sengottuvelan, Nallathambi;Yun, Seong-Jae;Kim, Dae-Young;Hwang, In-Hye;Kang, Sung Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.167-173
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    • 2013
  • A series of highly efficient red phosphorescent heteroleptic iridium(III) complexes 1-6 containing two cyclometalating 2-(2,4-substitued phenyl)quinoxaline ligands and one chromophoric ancillary ligand were synthesized: (pqx)$_2Ir$(mprz) (1), (dmpqx)$_2Ir$(mprz) (2), (dfpqx)$_2Ir$(mprz) (3), (pqx)$_2Ir$(prz) (4), (dmpqx)$_2Ir$(prz) (5), (dfpqx)$_2Ir$(prz) (6), where pqx = 2-phenylquinoxaline, dfpqx = 2-(2,4-diflourophenyl)quinoxaline, dmpqx = 2-(2,4-dimethoxyphenyl)quinoxaline, prz = 2-pyrazinecarboxylate and mprz = 5-methyl-2-pyrazinecarboxylate. The absorption, emission, electrochemical and thermal properties of the complexes were evaluated for potential applications to organic light-emitting diodes (OLEDs). The structure of complex 2 was also determined by single-crystal X-ray diffraction analysis. Complex 2 exhibited distorted octahedral geometry around the iridium metal ion, for which 2-(2,4-dimethoxyphenyl)quinoxaline N atoms and C atoms of orthometalated phenyl groups are located at the mutual trans and cis-positions, respectively. The emission spectra of the complexes are governed largely by the nature of the cyclometalating ligand, and the phosphorescent peak wavelengths can be tuned from 588 to 630 nm with high quantum efficiencies of 0.64 to 0.86. Cyclic voltammetry revealed irreversible metal-centered oxidation with potentials in the range of 1.16 to 1.89 V as well as two quasi-reversible reduction waves with potentials ranging from -0.94 to -1.54 V due to the sequential addition of two electrons to the more electron-accepting heterocyclic portion of two distinctive cyclometalated C^N ligands.

The Early Stages of Formation of the Passivation Film on Iron Electrode. Electrochemical and Automatic Ellipsometry Investigation (철전극 표면 부동화막의 생성과 초기단계의 변화)

  • In-Hyeong Yeo;Woon-Kie Paik
    • Journal of the Korean Chemical Society
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    • v.28 no.5
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    • pp.271-278
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    • 1984
  • Ellipsometric and reflectance measurements were made with magneto-optically self-nulling ellipsometer on the iron surface being passivated. The passivation was induced by abruptly changing potential of the mechanically polished high purity iron from the reduction potential to the oxidation potential in basic solutions. From the differences in the optical paramates(${\Delta},\;{\psi}$) and reflectance (R) between the reduced (film-free) and oxidized (film-covered) states, the thickness(${\tau}$) and optical constants (n, k) of the film in the early stage of its formation were computed as functions of pH and time. From the computed values, it was deduced that the properties of the anodic film did not undergo a drastic change with time which would indicate a transformation of the film before effective passivity is attained, and that the film reached its stady state within a few second. The thickness of anodic film was $14\;{\sim}\;23{\AA}$. The anodic films also seemed to have small values of optical absorption coefficient. The film formed in high pH environments had thinner and denser structure than that formed in low pH.

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The influence of preparation conditions on the electrochemical degradation of tungsten oxide thin films prepared by electron beam deposition (제작조건이 전자비임으로 제작된 텅스텐산화물 박막의 전기화학적 퇴화에 미치는 영향)

  • 이길동
    • Journal of the Korean Vacuum Society
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    • v.7 no.4
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    • pp.306-313
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    • 1998
  • The electrochromic $WO_3$thin films were prepared by using the electron-beam evaporatin technique. Flms prepared at a vacuum pressure of $10^{-4}$ mbar were found to be most stable during repeated potential cycles. The chemical stability of the film in aqueous solutions was also affected by the vacuum pressure during evaporation. The redox current and the optical properties of the degraded films were affected by the thickness of the film. The 5,000$\AA$-thick films were found to be most stable, undergoing the least degradation during the repeated coloring and bleaching cycles. The origin of the mechanism dominating the degradation during the repeated coloring and bleaching cycles was the accumulation of lithium in the film, which results in decreasing redox current. Tungsten oxide films with titanium content of about 10-15 mol% was found to be most stable, undergoing the least degradation during the repeated cycles. The origin of the mechanism dominating the least degradation during the repeated cycles was the reduction of lithium ion trapping sites in the films, which results in a increased durability.

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