Electrochemistry of Ruthenium Purple Confined in a Polymer Matrix: Voltammetry, Electrocatalysis for Hydrogen Evolution, and Electron-Transport Characteristics

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  • Toshiyuki Abe
    Department of Materials Science and Technology, Faculty of Science and Technology, Hirosaki UniversityHirosaki 036-8561
  • Noriaki Kawai
    Department of Materials Science and Technology, Faculty of Science and Technology, Hirosaki UniversityHirosaki 036-8561
  • Akio Tajiri
    Department of Materials Science and Technology, Faculty of Science and Technology, Hirosaki UniversityHirosaki 036-8561
  • Masao Kaneko
    Faculty of Science, Ibaraki UniversityMito 310-8512

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<jats:title>Abstract</jats:title> <jats:p>The synthesis of iron(III) ruthenocyanide (Ruthenium Purple, RP) in a Nafion (Nf) membrane was carried out. The visible-light absorption spectrum of the resulting RP exhibited an inter-valent charge-transfer band around 550–570 nm similar to that of neat RP, evidently showing that RP is formed in a polymer matrix. The voltammetric characteristics of the RP confined in the Nf matrix (Nf[RP]) were investigated compared with the neat RP. When Nf[RP] was used as an electrocatalyst to reduce H+, efficient H2 formation was found to originate from its molecular catalysis. In order to investigate the dominant factor that affects the overall kinetics in H+ reduction catalysis, the dependencies of both the catalytic activity (represented by the turnover number (TN) of a RP unit) and the diffusion coefficient of electron (Dapp) were studied as a function of the RP concentration in the matrix. The Dapp value decreased with increasing the concentration. The dependence of TN on the concentration was similar to that of Dapp, indicating that the overall kinetics is dominated by electron transport by RP.</jats:p>

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