Voltammetry at polymer-modified stationary and rotating microelectrodes. Application to determination of electron-transfer rates at polymer/solution interfaces

Thomas E. Mallouk, Vince Cammarata, Joseph A. Crayston, Mark S. Wrighton

Research output: Contribution to journalArticle

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Abstract

Voltammetric behavior of rotating disk and band microelectrodes with critical dimensions of 0.25-25 μm has been examined in solutions containing electroactive species. The microelectrode is fabricated to be in the plane but about 4 mm off the rotation axis of an insulating rotating disk. Such electrodes exhibit mass transport limited current densities which are 5-30 times higher than their macroscopic counterparts. This enhanced mass transport rate follows from equations previously derived for rotating ring electrodes. Rotating microelectrodes were functionalized with polymers derived from N,N′-bis((p-tri-methoxysilyl)benzyl)-4,4′-bipyridinium (I, [(BPQ2+)n]surf), N,N′-bis((trimethoxysilyl)propyl)-4,4′-bipyridinium (II, [(PQ2+)]surf), and 1,1′-bis[N-(3-(triethoxysilyl)propyl)carboxamide]cobalticenium (III, [Co(CpR)2 +]n,Surf). Steady-state currents, measured as a function of rotation rate for thermodynamically favored, polymer-mediated reductions of Ru(NH3)6 3+, Co(bpy)3 3+, and Cr3+-phenanthroline complexes, are in quantitative agreement with theory for such polymer-mediated redox processes. Values of rate constants for the polymer/redox couple electron-exchange reactions are found to be in the range 3 × 105 to >4 × 107 M-1 s-1. Rough agreement was found between measured rate constants and those calculated from the Marcus outer-sphere cross-reaction relation, although the calculated values were systematically higher.

Original languageEnglish (US)
Pages (from-to)2150-2156
Number of pages7
JournalThe Journal of Physical Chemistry
Volume90
Issue number10
DOIs
StatePublished - Jan 1 1986

Fingerprint

Microelectrodes
Voltammetry
Polymer solutions
Polymers
electron transfer
Electrons
rotating disks
polymers
Rotating disks
Rate constants
Mass transfer
Electrodes
axes of rotation
Phenanthrolines
electrodes
Current density
current density
rings
electrons
Oxidation-Reduction

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Mallouk, Thomas E. ; Cammarata, Vince ; Crayston, Joseph A. ; Wrighton, Mark S. / Voltammetry at polymer-modified stationary and rotating microelectrodes. Application to determination of electron-transfer rates at polymer/solution interfaces. In: The Journal of Physical Chemistry. 1986 ; Vol. 90, No. 10. pp. 2150-2156.
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Voltammetry at polymer-modified stationary and rotating microelectrodes. Application to determination of electron-transfer rates at polymer/solution interfaces. / Mallouk, Thomas E.; Cammarata, Vince; Crayston, Joseph A.; Wrighton, Mark S.

In: The Journal of Physical Chemistry, Vol. 90, No. 10, 01.01.1986, p. 2150-2156.

Research output: Contribution to journalArticle

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T1 - Voltammetry at polymer-modified stationary and rotating microelectrodes. Application to determination of electron-transfer rates at polymer/solution interfaces

AU - Mallouk, Thomas E.

AU - Cammarata, Vince

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AU - Wrighton, Mark S.

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N2 - Voltammetric behavior of rotating disk and band microelectrodes with critical dimensions of 0.25-25 μm has been examined in solutions containing electroactive species. The microelectrode is fabricated to be in the plane but about 4 mm off the rotation axis of an insulating rotating disk. Such electrodes exhibit mass transport limited current densities which are 5-30 times higher than their macroscopic counterparts. This enhanced mass transport rate follows from equations previously derived for rotating ring electrodes. Rotating microelectrodes were functionalized with polymers derived from N,N′-bis((p-tri-methoxysilyl)benzyl)-4,4′-bipyridinium (I, [(BPQ2+)n]surf), N,N′-bis((trimethoxysilyl)propyl)-4,4′-bipyridinium (II, [(PQ2+)]surf), and 1,1′-bis[N-(3-(triethoxysilyl)propyl)carboxamide]cobalticenium (III, [Co(CpR)2 +]n,Surf). Steady-state currents, measured as a function of rotation rate for thermodynamically favored, polymer-mediated reductions of Ru(NH3)6 3+, Co(bpy)3 3+, and Cr3+-phenanthroline complexes, are in quantitative agreement with theory for such polymer-mediated redox processes. Values of rate constants for the polymer/redox couple electron-exchange reactions are found to be in the range 3 × 105 to >4 × 107 M-1 s-1. Rough agreement was found between measured rate constants and those calculated from the Marcus outer-sphere cross-reaction relation, although the calculated values were systematically higher.

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