Effects of bridging ligands on the current - Potential behavior and interfacial kinetics of ruthenium-sensitized nanocrystalline TiO2 photoelectrodes

Kristine Kilså, Elizabeth I. Mayo, Darius Kuciauskas, Randy Villahermosa, Nathan S. Lewis, Jay R. Winkler, Harry B. Gray

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We have shown that RuII(bpy)2(bpy-4-(xylyl)x-≡-phenyl-COOH)( PF6)2 (abbreviated Rux, where x = 0, 1 or 2 xylyl groups; bpy = 2,2′-bipyridine) dyes can act as sensitizers for nanocrystalline TiO2 in functional photoelectrochemical cells under simulated solar illumination, albeit with low efficiencies. Both the short-circuit photocurrent density and the open-circuit voltage decreased as x was increased. Electron injection (106-108 s-1) was slightly faster for the x = 0 dye, but both recombination (10-1--10-13 cm3 s-1) and regeneration (104-106 s-1 for 10 mM I-) were slightly faster for the x = 2 dye. We suggest that the lack of distance dependence is due to the flexible one-carboxyl attachment to the surface resulting in the Ru-TiO2 electron-tunneling distance being very similar for x = 0, 1, and 2. For all of the Rux sensitizers, a relatively small potential was needed for generation of current in the dark, indicating that the reaction between electrons in TiO2 and the I3-/I- electrolyte solution is as favorable for the Rux sensitizers as for unmodified TiO2 electrodes.

Original languageEnglish
Pages (from-to)3379-3383
Number of pages5
JournalJournal of Physical Chemistry A
Issue number18
Publication statusPublished - May 8 2003


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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