EQCM investigations of dye-functionalized nanocrystalline titanium dioxide electrode/solution interfaces

Does luminescence report directly on interfacial electron transfer kinetics?

Buford I. Lemon, Joseph T Hupp

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Electrochemical quartz crystal microbalance (EQCM) experiments have been performed on dye-functionalized nanocrystalline titanium dioxide electrode/solution interfaces. The experiments show that reversible, potential-induced dye desorption occurs in both aqueous and nonaqueous environments at potentials close to the conduction band edge. Previous experiments have reported that potentiostatic filling of empty conduction band or near-band-edge surface states has dramatic effects on the corresponding photophysical and photochemical behavior of surface-bound dyes. Most notably, apparent decreases in the efficiencies of charge injection and increases in dye luminescence yield were found to accompany potential changes. Detailed analyses have emphasized the role of surface-state filling in decreasing the driving force for injection processes and thus, increasing the luminescence quantum yield. The electrochemically stimulated dye detachment phenomenon reported here provides a compelling alternative or additional mechanistic explanation for the profound potential dependence of the interfacial luminescence responses.

Original languageEnglish
Pages (from-to)3798-3799
Number of pages2
JournalJournal of Physical Chemistry B
Volume103
Issue number19
Publication statusPublished - 1999

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Quartz crystal microbalances
quartz crystals
titanium oxides
microbalances
Titanium dioxide
Luminescence
electron transfer
Coloring Agents
Dyes
dyes
luminescence
Electrodes
Kinetics
electrodes
Electrons
kinetics
Surface states
Conduction bands
conduction bands
injection

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Cite this

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abstract = "Electrochemical quartz crystal microbalance (EQCM) experiments have been performed on dye-functionalized nanocrystalline titanium dioxide electrode/solution interfaces. The experiments show that reversible, potential-induced dye desorption occurs in both aqueous and nonaqueous environments at potentials close to the conduction band edge. Previous experiments have reported that potentiostatic filling of empty conduction band or near-band-edge surface states has dramatic effects on the corresponding photophysical and photochemical behavior of surface-bound dyes. Most notably, apparent decreases in the efficiencies of charge injection and increases in dye luminescence yield were found to accompany potential changes. Detailed analyses have emphasized the role of surface-state filling in decreasing the driving force for injection processes and thus, increasing the luminescence quantum yield. The electrochemically stimulated dye detachment phenomenon reported here provides a compelling alternative or additional mechanistic explanation for the profound potential dependence of the interfacial luminescence responses.",
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AU - Lemon, Buford I.

AU - Hupp, Joseph T

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AB - Electrochemical quartz crystal microbalance (EQCM) experiments have been performed on dye-functionalized nanocrystalline titanium dioxide electrode/solution interfaces. The experiments show that reversible, potential-induced dye desorption occurs in both aqueous and nonaqueous environments at potentials close to the conduction band edge. Previous experiments have reported that potentiostatic filling of empty conduction band or near-band-edge surface states has dramatic effects on the corresponding photophysical and photochemical behavior of surface-bound dyes. Most notably, apparent decreases in the efficiencies of charge injection and increases in dye luminescence yield were found to accompany potential changes. Detailed analyses have emphasized the role of surface-state filling in decreasing the driving force for injection processes and thus, increasing the luminescence quantum yield. The electrochemically stimulated dye detachment phenomenon reported here provides a compelling alternative or additional mechanistic explanation for the profound potential dependence of the interfacial luminescence responses.

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