New strategies for electrocatalysis at polymer-coated electrodes. Reduction of dioxygen by cobalt porphyrins immobilized in nafion coatings on graphite electrodes

Daniel Buttry, Fred C. Anson

Research output: Contribution to journalArticle

161 Citations (Scopus)

Abstract

A new method for introducing porphyrin molecules into Nafion coatings on electrodes is described. The incorporated porphyrins are exceptionally stable and can readily be metallated while remaining in the coating. Coatings containing cobalt tetraphenylporphyrin (CoTPP) were prepared to exemplify the method, which is applicable to a variety of macrocyclic ligands possessing basic sites. The CoTPP in the Nafion coatings retained its ability to catalyze the electroreduction of dioxygen when the electrons were carried from the electrode to the almost immobile catalyst sites by Ru(NH3)6 2+ ions also incorporated in the coating. The resulting separation of the catalytic and electron transport functions within such coatings is argued to have general virtues that may be exploited to extend the range of applicability of polymer-coated electrodes in electrocatalysis and to diagnose the mechanisms by which they operate.

Original languageEnglish (US)
Pages (from-to)59-64
Number of pages6
JournalJournal of the American Chemical Society
Volume106
Issue number1
StatePublished - 1984
Externally publishedYes

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Electrocatalysis
Graphite electrodes
Graphite
Porphyrins
Cobalt
Polymers
Electrodes
Oxygen
Coatings
Aptitude
Electron Transport
Electrons
Ions
Ligands
perfluorosulfonic acid
Catalysts
Molecules
tetraphenylporphyrin

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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AU - Anson, Fred C.

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N2 - A new method for introducing porphyrin molecules into Nafion coatings on electrodes is described. The incorporated porphyrins are exceptionally stable and can readily be metallated while remaining in the coating. Coatings containing cobalt tetraphenylporphyrin (CoTPP) were prepared to exemplify the method, which is applicable to a variety of macrocyclic ligands possessing basic sites. The CoTPP in the Nafion coatings retained its ability to catalyze the electroreduction of dioxygen when the electrons were carried from the electrode to the almost immobile catalyst sites by Ru(NH3)6 2+ ions also incorporated in the coating. The resulting separation of the catalytic and electron transport functions within such coatings is argued to have general virtues that may be exploited to extend the range of applicability of polymer-coated electrodes in electrocatalysis and to diagnose the mechanisms by which they operate.

AB - A new method for introducing porphyrin molecules into Nafion coatings on electrodes is described. The incorporated porphyrins are exceptionally stable and can readily be metallated while remaining in the coating. Coatings containing cobalt tetraphenylporphyrin (CoTPP) were prepared to exemplify the method, which is applicable to a variety of macrocyclic ligands possessing basic sites. The CoTPP in the Nafion coatings retained its ability to catalyze the electroreduction of dioxygen when the electrons were carried from the electrode to the almost immobile catalyst sites by Ru(NH3)6 2+ ions also incorporated in the coating. The resulting separation of the catalytic and electron transport functions within such coatings is argued to have general virtues that may be exploited to extend the range of applicability of polymer-coated electrodes in electrocatalysis and to diagnose the mechanisms by which they operate.

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