Surface Electrochemistry of Chloro(phthalocyaninato)rhodium(III) Species and Oxygen Reduction Electrocatalysis. Formation of a Dimeric Species

Yu Hong Tse, Penny Seymour, Herman Lam, Clifford C. Leznoff, A. B.P. Lever, Nagao Kobayashi

Research output: Contribution to journalArticlepeer-review

32 Citations (Scopus)

Abstract

The deposition of chloro(phthalocyaninato)rhodium(III) onto a highly oriented pyrolytic graphite (HOPG) electrode leads to a surface which can be organized by polarizing to potentials negative of the reduction of rhodium(III) to rhodium(II). The organized surface contains dinuclear rhodium phthalocyanine, which is fairly stable in its [RhIIPc]2 oxidation state. It is reversibly oxidized to a [RhIII, Pc]2 dinuclear species, which decomposes slowly to monomeric RhIIIPc, detected upon the surface through its electroactivity. Reduction of mononuclear RhIIIPc back to RhIIPc leads to redimerization. The surface electrochemistry of this dynamic interplay between mononuclear and dinuclear species is explored in depth. The dinuclear [RhIIPc]2 species reacts with oxygen to form oxygen adducts, which appear to be involved in both the 2-electron reduction of oxygen to hydrogen peroxide and the 4-electron reduction to water. However, these two processes proved difficult to characterize.

Original languageEnglish
Pages (from-to)4453-4459
Number of pages7
JournalInorganic chemistry
Volume30
Issue number23
DOIs
Publication statusPublished - 1991 Nov 1

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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