• Journal of the Korean Electrochemical Society
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• v.4 no.1
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• pp.14-20
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• 2001

The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the single crystal Pt(100)/0.5 M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using the phase-shift method. The phase-shift profile $({-\varphi}\;vs.\;E)$ for the optimum intermediate frequency can be used as a useful method to estimate the Langmuir adsorption isotherm $(\theta\;vs.\;E)$ at the interfaces. The equilibrium constant (K) for the OPD H and the standard free energy $({\Delta}G_{ads})$ of the OPD H at the Pt(100)/0.5M $H_2SO_4$ aqueous electrolyte interface are $1.5\times10^{-4}$ and 21.8 kJ/mol, respectively. At the Pt(100)/0.5 LiOH aqueous electrolyte interface, K transits from 1.9(UPD H) to $6.8\times10^{-6}$(OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits -1.6 kJ/mol (UPD H) to 29.5 kJ/mol (OPD H) depending on E and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and OPD H on the Pt(100) surface. The UPD H and the OPD H at the Pt(100) interfaces are the independent processes depending on the H adsorption sites rather than the sequential processes for the cathodic $H_2$ evolution reactions.

• Journal of the Korean Electrochemical Society
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• v.5 no.3
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• pp.131-142
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• 2002

The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

• Journal of the Korean Electrochemical Society
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• v.2 no.1
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• pp.23-26
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• 1999

The Langmuir adsorption isotherm at the $(Pt)/0.1M\;H_2SO_4$ electrolyte interface has been qualitatively analyzed using the ac impedance measurement and phase-shift method. The phase shift $(\phi)$ depends on both the cathode potential (E<0) and frequency (f) and is inversely proportional to the factional surface coverage $(\theta)$. At an intermediate frequency band (ca. $1\~100$ Hz), the phase-shift profile $(\phi\;vs.\;E)$ can be related to the fractional surface coverage $(\theta\;vs.\;E)$. The phase-shift profile $(\phi\;vs.\;E)$ can be used as an experimental method to estimate and analyze the Langmuir adsorption isotherm $(\theta\;vs.\;E)$. The equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the adsorbed hydrogen atom $(H_{ads})\;and\;3\times10^{-4}$ and 20.1 kJ/mol, respectively.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.371-378
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• 1989

Kinetics of the substitution reaction of [pt[dien]X]$^+$(X = $Cl^-$, $Br^-$, $I^-$) with NO2- in aqueous solution were investigated by a spectrophotometric method at $20-35^{\circ}C$ and 1-1500 bars. The rates of these reactions were increased with raising temperature and pressure. The relative reactivities of replaceable ligands in [pt[dien]X]$^+$ follow the order ($Cl^-$ > $Br^-$ > $I^-$). Activation volumes (${\mid}{\Delta}V^{\neq}{\mid}$) were large negative values and decreased with raising temperature. First ($k_1$) and second($k_2$) order rate constants of these reactions were determined at $25^{\circ}C$ and both $k_1$ and $k_2$ were increased with raising pressure and activation volumes (${\Delta}{V_1}^{\neq}$, ${\Delta}{V_2}^{\neq}$) for the $k_1$ and $k_2$ path were large negative values respectively. The $k_1$ and $k_2$ of these reactions were determined at 1 bar and these values were increased with raising temperature. Activation parameters of $k_1$ and $k_2$ path were determined, therefore it can be inferred frp, these results that the substitution reactions of [pt[dien]X]$^+$ with ${NO_2}^-$ proceed through on associative (A) mechanism independent of a leaving groups and reaction paths.

• Korean Journal of Materials Research
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• v.6 no.8
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• pp.825-832
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• 1996

적외선 센서의 재료로 활용되고 있는 PLT박막 (두께:8000$\AA$-9000$\AA$)을 Pt/Ti/SiO2/Si와 Pt/M\ulcorner의 하부 구조상에 50$0^{\circ}C$, 55$0^{\circ}C$ 및 $600^{\circ}C$에서 스퍼터링 증착하여 결정성 및 전기적 특성을 조사하였다. $600^{\circ}C$로 in-situ 성장된 PLT박막은 Si기판을 이용한 경우 randomly oriented perovskite 결정구조를 나타내었으며, Pt/MgO 구조위에서는 c-축(00ι)방향으로 배향 성장되었다. $600^{\circ}C$에서 in-situ 성장된 PLT박막의 비유전상수($\varepsilon$r)와 유전정접(tan $\delta$)을 10kHz-100kHz의 주파수에서 측정한 결과 Pt/Ti/SiO2/Si 구조상에 증착된 박막은$\varepsilon$r=90과 tan $\delta$=0.02의 값을 Pt/MgO 구조상에 증착된 박막은 $\varepsilon$e=35와 tan$\delta$=0.01의 값을 나타내었다. 잔류분극량(2Pr)과 초전계수(${\gamma}$)는 상온부근에서 Si 기판을 이용한 경우 각각 0.6$\mu$C/$\textrm{cm}^2$.。C과 0.5x10-8C/$\textrm{cm}^2$.。C정도로 매우 작게 나타났으나 PLT/Pt/MgO 구조에서는 2Pr=5$\mu$C/$\textrm{cm}^2$, r=4x10-8C/$\textrm{cm}^2$.。C로 비교적 양호한 초전박막의 전기적 특성을 나타내었다.

• Bulletin of the Korean Chemical Society
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• v.6 no.4
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• pp.214-217
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• 1985

Platinum(II) complexes of R-2,2'-diaminobinaphthyl (R-dabn), [Pt(R-dabn)(H2O)2]Cl2, [Pt(R-dabn)(R-Pn)]Cl2, [Pt(R-dabn)(R-bn)]Cl2, and platinum(II) complexes of S-2,2'-diaminobinaphthyl (S-dabn), [Pt(S-dabn)(H2O)2]Cl2, [Pt(S-dabn)(S-Pn)]Cl2, and [(Pt(S-dabn)(S-bn)]Cl2 have been prepared. (R-Pn and S-Pn are, respectively R- and S isomer of 2,3-diaminobutane). R-Pn and S-bn are, respectively R and S isomer of 2,3-diaminopropane). In the vicinity of the B-absorption band region of dabn, the circular dichroism spectra of platinum(Ⅱ) complexes of R-dabn series show a positive B-band followed by a negative higher energy A-band, which is generally understood as the splitting pattern for a ${\lambda}$ conformation, while the circular dichroism spectra of platinum(Ⅱ) complexes of S-dabn series show a negative B-band followed by a positive higher energy A-band in the long-axis polarized absorption region as expected for a $\delta$ conformation.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2010.06a
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• pp.214-214
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• 2010

The 0.65Pb($Mg_{1/3}Nb_{2/3})O_3-0.35PbTiO_3$ (PMN-PT) thin films with $La_{0.5}Sr_{0.5}CoO_{3-\delta}$ (LSCO) bottom electrodes were grown on $CeO_2$/YSZ/Si(001), Pt/$TiO_2$/Si and $SrTiO_3$ (STO) substrates using conventional pulsed laser deposition (PLD) at a substrate temperature of $550^{\circ}C$. Since generally the crystallographic orientation of the bottom electrode induces the orientation of the films deposited on it, it allows us to observe the influence of the PMN-PT film orientation on the electrical properties. Phi scan done on PMN-PT/LSCO thin films shows epitaxial behavior of the films grown on sto substrates and $CeO_2$/YSZ buffered Si(001) substrates, and (110) texture on Pt/$TiO_2$/Si substrates. Polarization-electricfield (P-E) measurement shows good hysteresis behavior of PMN-PT films with remnant polarization of 18.2, 8.8, and $4.4{\mu}C/cm^2$ on $CeO_2$/YSZ/Si, Pt/TiO2/Si and STO substrates respectively.

• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.369-377
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• 1998

The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.

• Journal of the Korean Electrochemical Society
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• v.2 no.4
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• pp.213-217
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• 1999

The electrochemical characteristics of two distinct adsorption sites of H at the polycrystalline Pt/0.2 M LiOH aqueous electrolyte interface have been studied using the phase-shift method. At the forward and backward scans, the under-potentially deposited H (WD H) peak occurs on the cyclic voltammogram. The transition region on the phase-shift profile or the Langmuir adsorption isotherm occurs at ca. -0.66 to -0.96 V vs. SCE. At the transition region (ca. -0.66 to -0.96 V vs. SCE), the equilibrium constant (K) for H adsorption transits from 18.5 to $4.0\times10^{-5}$ and vice versa. Similarly, the standard free energy $({\Delta}G_{ads})$ of H adsorption transits from -7.2 to 25.1kJ/mol and vice versa. The under and over-potentially deposited H (UPD H and OPD H) on the poly-Pt surface act as two distinguishable electroadsorbed H species. An exothermic reaction occurs at the UPD H range. Both the UPD H peak and the transition region are attributed to the two distinct adsorption sites of the UPD H and OPD H on the poly-Pt surface.

• Korean Journal of Materials Research
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• v.9 no.5
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• pp.484-490
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• 1999

$(Pb,La)TiO_3$(PLT) thin films were prepared on Pt/SiO$_2$/Si substrates by the sol-gel method and investigated the crystalline and electrical properties according to La concentration and post-annealing temperatures. The PLT films annealed at above $600^{\circ}C$ were exhibited the typical perovskite structures regardless of La contents. When the $(Pb,La)TiO_3$(PT) films were doped with La concentration up to 10mol%(PLT-10), the degree of z-axis orientation was greatly decreased from 63% to 26%. From AES depth profiles for the PLT-10 samples, no remarkable inter-reaction between PLT film and lower Pt electrode was found. The remanent polarization$(2Pr,Pr_+-Pr_-)$ were increased from $4\muC\textrm{cm}^2 to 16\muC\textrm{cm}^2$ as the annealing temperature increased from $600^{\circ}C to 700^{\circ}C$. This result may be ascribed to the improvement of crystallinity by the high temperature post-annealing. The dielectric constant$({\varepsilon}r)$ and tangent loss(tan$\delta$) of the PLT-10 films annealed at $650^{\circ}C$ were about 193 and 0.02, respectively with the pyroelectric coefficient($\gamma$) of around $4.0nC/\textrm{cm}^2{\cdot}^{\circ}C at 30^{\circ}C$.