Effects of electron trapping and protonation on the efficiency of water-splitting dye-sensitized solar cells

John R. Swierk, Nicholas S. McCool, Timothy P. Saunders, Greg D. Barber, Thomas E. Mallouk

Research output: Contribution to journalArticlepeer-review

78 Scopus citations


Water-splitting dye-sensitized photoelectrochemical (WS-DSPECs) cells employ molecular sensitizers to absorb light and transport holes across the TiO2 surface to colloidal or molecular water oxidation catalysts. As hole diffusion occurs along the surface, electrons are transported through the mesoporous TiO2 film. In this paper we report the effects of electron trapping and protonation in the TiO2 film on the dynamics of electron and hole transport in WS-DSPECs. When the sensitizer bis(2,2′-bipyridine)(4,4′-diphosphonato-2,2′-bipyridine) ruthenium(II) is adsorbed from aqueous acid instead of from ethanol, there is more rapid hole transfer between photo-oxidized sensitizer molecules that are adsorbed from strong acid. However, the photocurrent and open-circuit photovoltage are dramatically lower with sensitizers adsorbed from acid because intercalated protons charge-compensate electron traps in the TiO2 film. Kinetic modeling of the photocurrent shows that electron trapping is responsible for the rapid electrode polarization that is observed in all WS-DSPECs. Electrochemical impedance spectroscopy suggests that proton intercalation also plays an important role in the slow degradation of WS-DSPECs, which generate protons at the anode as water is oxidized to oxygen.

Original languageEnglish (US)
Pages (from-to)10974-10982
Number of pages9
JournalJournal of the American Chemical Society
Issue number31
StatePublished - Aug 6 2014

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


Dive into the research topics of 'Effects of electron trapping and protonation on the efficiency of water-splitting dye-sensitized solar cells'. Together they form a unique fingerprint.

Cite this