• Title/Summary/Keyword: H-PT

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Direct Conversion of Cellulose into Polyols over Pt/CsxH3-xPW12O40

  • You, Su Jin;Baek, In Gu;Park, Eun Duck
    • Clean Technology
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    • v.19 no.1
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    • pp.13-21
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    • 2013
  • The hydrogenolysis of cellulose into polyols was examined over Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts containing different Cs fractions. The surface area and Pt dispersion of Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts were found to increase with Cs content. Similar polyol yields were obtained over Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts irrespective of their Cs content. The catalytic activity of Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ was comparable to that of Ni/W/SBA-15 and combined catalytic systems such as Pt/AC+$H_3PW_{12}O_{40}$ and Pt/AC + $Cs_{3.0}PW_{12}O_{40}$. Some polyanion species were found to leach from the Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalyst during the course of the reaction.

Potential Energy Surfaces for Ligand Exchange Reactions of Square Planar Diamagnetic PtY2L2 Complexes:Hydrogen Bond (PtY2L2···L') versus Apical (Y2L2Pt···L') Interaction

  • Park, Jong-Keun;Kim, Bong-Gon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1405-1417
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    • 2006
  • The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

Effect of Temperature on $H_2$ Spillover over $Pt/H_xMoO_3$ (Pt를 담지한 $H_xMoO_3$촉매의 수소 이동 속도에 미치는 온도의 영향)

  • 김진걸
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.5 no.2
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    • pp.114-117
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    • 2004
  • Rates of $H_2$ uptake into $Pt/MoO_3$ were measured for the noncalcined and $200^{\circ}C$ calcined $Pt/MoO_3$. Amount of $H_2$ uptake for $200^\circ{C}$calcined $Pt/MoO_3$ was greater than the amount of noncalcined $Pt/MoO_3$. From these two experiments, it was found that the rates of $H_2$ desorption were proportional to the increase of desorption temperature. XPS demonstrated that Cl reduced more faster in ITR after calcination at $200^{\circ}C$. This inducd smaller amount of residual chlorine at adlineation sites between Pt and $MoO_3$ substrates. This resulted in opening the more channel of hydrogen pathway into more $MoO_3$particles and controled the kinetics of hydrogen uptake.

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Effect of MoO3 Morphological Change over Hydrogen Spillover Kinetics (MoO3 Morphology 변화가 수소 Spillover에 미치는 영향)

  • Kim, Jin Gul
    • Applied Chemistry for Engineering
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    • v.10 no.8
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    • pp.1109-1113
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    • 1999
  • sothemal reduction at $50^{\circ}C$ using $Pt/MoO_3$ or $Pt/MoO_3/SiO_2$ made by dry impregnation or physical mixture of $Pt^{\circ}$ and $MoO_3$ demonstrated that the $H_2$ uptake vis $H_2$ spillover from Pt into $MoO_3$ was enhanced as calcination temperature was increased. Surface area of exposed Pt crystallites measured by CO chemisorption was decreased with higher calcination temperature. In addition, TEM showed that $MoO_x$ overlayers were formed on Pt crystallites after calcination at $400^{\circ}C$. Consequentially, it was found that this increased active contact sites between Pt and $MoO_3$ due to surface morphological change was one of the dominant factors for this increased $H_2$uptake via $H_2$ spillover from Pt crystallites into $MoO_3$.

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Determination of the Frumkin and Temkin Adsorption Isotherms of Underpotentially Deposited Hydrogen at Pt Group Metal Interfaces Using the Standard Gibbs Energy of Adsorption and Correlation Constants

  • Chun, Jinyoung;Jeon, Sang K.;Chun, Jang H.
    • Journal of the Korean Electrochemical Society
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    • v.16 no.4
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    • pp.211-216
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    • 2013
  • At Pt(111), Pt(100), Pt, and Rh interfaces, the Frumkin adsorption isotherm of underpotentially deposited hydrogen (UPD H) and related electrode kinetic data are determined using the standard Gibbs energy of adsorption. The Temkin adsorption isotherm of UPD H correlating with the Frumkin adsorption isotherm of UPD H is readily determined using the correlation constants between the Temkin and Frumkin or Langmuir adsorption isotherms. At the Pt(111), Pt(100), Pt, and Rh interfaces, the lateral repulsive interaction between the UPD H species is interpreted using the interaction parameter for the Frumkin adsorption isotherm. The lateral repulsive interaction between the UPD H species at the Pt(111), Pt(100), Pt, and Rh interfaces is significantly different from the lateral attractive interaction between the overpotentially deposited hydrogen (OPD H) species at Pt, Ir, and Pt-Ir alloy interfaces.

Oxidation characterization of VOCs over noble metal catalyst using water treatment (Water 수처리를 이용한 귀금속 촉매의 VOCs 산화특성)

  • Kim, Moon-Chan
    • Analytical Science and Technology
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    • v.18 no.2
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    • pp.120-129
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    • 2005
  • Volatile organic compounds (VOCs) have been recognized as major contributor to air pollution. The catalytic oxidationis is one of the most important processes for VOCs destruction due to the possibility getting high efficiency at low temperature. In this study, monometallic Pt, Ir and bimetallic Pt-Ir were supported to $TiO_2$. In order to distribute metals uniformly, $H_2O-H_2$ treatment method was used. Xylene, toluene and MEK were used as reactants. The monometallic or bimetallic catalysts were prepared by the excess wetness impregnation method and characterized by XRD, XPS, and TEM analysis. Pt catalyst showed higher conversion than Ir catalyst and Pt-Ir bimetallic catalyst showed the highest conversion. The catalysts prepared by $H_2O-H_2$ treatment had better VOC's conversion than that of nothing treatment. In the VOCs oxidation, Pt-Ir bimetallic catalysts had multipoint active sites, so it improved the range of Pt metal state. Therefore, bimetallic catalysts showed higher conversion of VOCs than monometallic ones. $H_2O-H_2$ treatment effected an uniform distribution of Pt particles. In VOCs oxidation was found to follow first order reaetion kinetics. The activation energy of $H_2O-H_2$ treatment catalysts was lower than that of untreated ones. In this study, the a small amount of Ir was used with Pt to promote the oxidation conversion of VOCs.

Solid-State $^{31}P$ NMR Chemical Shielding Tensors in Binuclear Platinum Diphosphite Complexes

  • 우애자;Leslie G. Butler
    • Bulletin of the Korean Chemical Society
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    • v.17 no.5
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    • pp.457-460
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    • 1996
  • The principal elements of the 31P NMR chemical shielding tensors have been determined for three binuclear platinum diphosphite complexes, K4[Pt2(P2O5H2)4·2H2O ("Pt2"), K4[Pt2(P2O5H2)4Cl2]·2H2O ("Pt2Cl2"), and K4[Pt2(P2O5H2)4Br2]·2H2O ("Pt2Br2"), by using a Herzfeld-Berger graphical method for interpreting the 31P MAS spectrum. The orientations of 31P chemical shielding tensor relative to the molecular axis system are partially assigned with combination of the longitudinal relaxation study of HPO32- and the reference to known tensor orientations of related sites; the most chemical shielding component, δ33, is directed along the P-Pt bond axis. A discussion is given in which the experimental principal elements of the 31P chemical shielding tensor are related with the Pt-Pt bond distances in binuclear platinum diphosphite complexes.

Durability of Xenograft Cardiac Valves (이종조직 판막의 내구성)

  • 김종환
    • Journal of Chest Surgery
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    • v.25 no.5
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    • pp.494-503
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    • 1992
  • The durability of the xenograft cardiac substitute valves is of a great concern on the clinical grounds. Four groups of tc tal and consecutive patients to the end of study operated on between 1976 and 1984 were Group ISM, 291 patients of MVR, ISA, 65 patients of AVR, and ISMA, 107 patients of MVR+AVR with the standard Ionescu-Shiley bovine pericardial valve, and H, 163 patients of valve replacement with the Hancock porcine aortic vlave. Operative mortality was 5.2%[ISM], 10.8%[ISA], 7.5%[ISMA] and 6.1%[H]. Early survivors were followed up for a total of 1148.3 patient-years[pt-yrs] [ISM], 271.2 pt-yrs [ISA], 488.1 pt-yrs[ISMA] and 822.9 pt-yrs[H]. Linearized late mortality was 2.1% /pt-yr [ISM], 1.l%/pt-yr[ISA], 1.8%/pt-yr[ISMA] and 1.8% /pt-yr[H]. Thromboembolic complication was experienced at the linearized rate of 1.045% /pt-yr [ISM], 1.475%/pt-yr[ISA], 0.615%/pt-yr[ISMA] and 1.822%/pt-yr[H], and bleeding complication at the rate of 0.871% /pt-yr[ISM], 0.63% /pt-yr[ISA], 0.205% /pt-yr [ISMA] and 0.729%a /pt-yr[H], respectively. Prosthetic valve endocarditis occurred at the rate of 0.610% /pt-yr[ISM], 1.475% /pt-yr[ISA], 1.639% /pt-yr[ISMA] and 0.972% /pt-yr[H]. The linearized annual incidence of primary tissue failure was 1.655%/pt-yr[ISM], l. 475%/pt-yr[ISA], 1.639% /pt-yr[ISMA], 2.187% /pt-yr[H] and 1.785% /pt-yr[Group HM : MVR with Hancock valve]. The incidence of tissue failure was significantly high in the patients younger than 30 years of age compared with the older patients. The actuarial survival was 87.7$\pm$2.5% at 10 years[ISM], 94.3$\pm$3.2% at 11 years[ISA], 89.6$\pm$3.4% at 10 years[ISMA] and 81.3$\pm$6.6% at 12 years[HM], The freedom from thromboembolism was 93.2$\pm$2.0% at 10 years[ISM], 90.6$\pm$4.6% at 11 years[ISA], 95.8$\pm$2.6% at 10 years[ISMA] and 80.9$\pm$11.1% at 12 years[HM], And, the freedom from primary tissue failure was 84.2$\pm$3.8% and 28.1$\pm$23.0% at 9 and 10 years[ISM], 60.4$\pm$16.9% at 11 years[ISA], 62.3$\pm$12.7 at 10 years[ISMA] and 65.6$\pm$9.8% at 12 years[HM]. In conclusion, the standard Ionescu-Shiley and the Hancock bioprosthetic valves are excellent in their antithrombogenicity and long-term survival. However, the features of the structural failure with the prolonged follow-up beyond 10 years appear to be guarding, and the clinical indications of these bioprostheses seem to be quite limited.

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Amine and Olefin Complexes of Pt(II) Having a PCP-Pincer Ligand

  • Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.132-136
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    • 2002
  • $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

Effects of Pretense Treatment on Functional Properties of Soymilk Protein (단백분해 효소처리가 두유단백질의 기능성에 미치는 영향)

  • 변진원;황인경
    • Korean journal of food and cookery science
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    • v.11 no.1
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    • pp.26-32
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    • 1995
  • This study was carried out to investigate the effect of protease on the functionality of soymilk protein. The protease from Bacillus polymyxa was selected because of the least production of bitter taste and calcium-aggregation. The results are summarized as follows: 1. Solubility of SMP(soymilk protein) and SPI(soyprotein isolate) were lowest at pH 4.7 and increased as the pH value reached closer to either ends. PT-SMP(pretense treated soymilk protein) showed higher solubility at all pH range, especially at pH 4.7 than SMP, SPI. 2. Emulsion activity of three samples was lowest at pH 4.7 and significantly increased as pH approched higher acidic or alkaline regions. PT-SMP showed similar activity to other samples, but less stability. 3. Foam capacity of PT-SMP was lowest at pH 8 and increased in acidic, alkaline pH. PT-SMP showed higher foam capacity at all pH range, but lower foam stability than SMP and SPI. 4. PT-SMP showed higher heat coagulability than other samples at all pH range except pH 4.7.

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