Revealing the nature of trapping sites in nanocrystalline titanium dioxide by selective surface modification

Nada M. Dimitrijevic, Zoran V. Saponjic, David M. Bartels, Marion C. Thurnauer, David M. Tiede, Tijana Rajh

Research output: Contribution to journalArticlepeer-review

93 Scopus citations


Excess electrons in nanocrystalline TiO2 were studied in bare and dopamine-capped TiO2 nanoparticles by electron-beam pulse radiolysis. Reaction of hydrated electrons with dopamine-capped TiO2 nanoparticles was found to be at the diffusion-controlled limit, k = 1 × 1011 M-1 s-1, while the reaction with 1-hydroxy-1-methylethyl radicals, (CH3)2COH, was 2 orders of magnitude slower, k = 4 × 108 M-1 s-1. The reactions result in injection of electrons into the conduction band of TiO2 nanoparticles. Optical absorption spectra of injected excess electrons in dopamine-capped nanoparticles display monotonic featureless wavelength dependence up to 1800 nm. In contrast, bare particles have shown two preferential optical transitions with energies in the visible region (λmax = 670 nm and λmax = 900 nm). Flat band potential of dopamine-capped TiO2 nanoparticles was shifted by 100 mV to more negative values. The strong coupling of dopamine to surface Ti atoms was also found to improve the separation of photogenerated charges. This was demonstrated by the enhanced efficiency of photogenerated electrons in reducing silver cations to metallic silver in systems linked via a dopamine bridge, compared to the same systems linked through carboxyl groups.

Original languageEnglish (US)
Pages (from-to)7368-7375
Number of pages8
JournalJournal of Physical Chemistry B
Issue number30
StatePublished - Jul 31 2003
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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