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Research on Chemical Intermediates

, Volume 20, Issue 8, pp 879–892 | Cite as

Decay of Ru(BPY)3 3+ in thin nafion layers catalyzed by Co(II)

  • Joseph Rabani
  • Tsukada Yoshida
  • Masao Kaneko
  • Akira Kira
Article
  • 24 Downloads

Abstract

Catalytic oxidation of water by Ru(bpy)3 3+ in the presence of Co2+ ions, well known in homogeneous solution, has been investigated in thin Nafion layers. Nafion layers on ITO electrodes were equilibrated with Ru(bpy)3 2+. Ru(bpy)3 3+ was produced by electrochemical oxidation after which the electrode was transferred into the reaction cell containing buffered Co2+ solution. The build up of Ru(bpy)3 2+ absorbance at 454 nm was followed spectrophotometrically. The reaction rate is proportional to [Ru(III)], [Co2+] and [HPO4 2-]. We found no evidence for a pH effect in the range 6–8, and no inhibition by Ru(II). A limiting rate of formation of Ru(II) is observed at high Co2+ or phosphate ion concentrations. At high local concentration of the Ru complex in the Nafion layer (~ 0.5 M), two Ru(II) formation processes are observed, their rates differ by one order, but other features (effects of [Ru(III)], [Ru(II)], [Co2+], phosphate and pH) remain unchanged. These results are in contrast with homogeneous solution where the rate of build up of Ru(II) has been previously reported to be proportional to [Ru(III)], [Co2+] and [OH-]2, and inversely proportional to [Ru(II)]. A mechanism is proposed which accounts for these observations.

Keywords

Phosphate Concentration Order Rate High Local Concentration Nation Layer Rhenium Oxide 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© VSP 1994

Authors and Affiliations

  • Joseph Rabani
    • 1
  • Tsukada Yoshida
    • 2
  • Masao Kaneko
    • 2
  • Akira Kira
    • 2
  1. 1.Farkas Centre, Department of Physical ChemistryThe Hebrew UniversityJerusalemIsrael
  2. 2.Chemical Dynamics LaboratoryThe Institute of Physical and Chemical Research (Riken)Wako, SaitamaJapan

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