Narrow-band irradiation of a homologous series of chlorophenols on TiO 2: Charge-transfer complex formation and reactivity

Alexander G. Agrios, Kimberly A Gray*, Eric Weitz

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

80 Scopus citations


The goal of this research was to investigate the formation and reactivity of charge-transfer complexes (CTCs) among a homologous series of chlorophenols on TiO 2. We previously showed that 2,4,5-trichlorophenol (245TCP) forms a CTC with Degussa P25, a commercial preparation of TiO 2. Here, we probe how light energy influences reactivity and product formation, Slurries of P25 containing 245TCP were irradiated at 360,400,430,480, and 550 nm. At each wavelength, the amount of transformation of 245TCP correlates to the diffuse-reflectance absorbance of a 245TCP/P25 system, supporting the CTC as the cause of reaction, In addition, polymeric products are formed only under wavelengths that excite the CTC, indicating a different reaction mechanism for the CTC than for bandgap excitation of TiO 2. We also found a higher quantum efficiency for CTC reactivity than for bandgap activation of the catalyst, suggesting that the photocatalytic efficiency and selectivity can be improved for certain compounds by designing catalytic materials that form CTCs with them. Furthermore, to determine how chlorine substitution patterns affected adsorption and sub-bandgap reactivity, P25 slurries containing phenol, 4-chlorophenol, 2,4-dichlorophenol, or 2,4,6-trichlorophenol were probed following dark contact or irradiation at 360, 430, or 550 nm. With respect to the extent of adsorption, complexation, reaction, and polymerization on P25, the behavior of 245TCP far exceeded that of the other chlorophenols. Among these chlorophenols, only 2,4-dichlorophenol produced a polymeric product. 245TCP is unique among this family of chlorophenols, which we attribute to a chlorine arrangement that leads to a favorable orbital overlap with TiO 2 and sterically permits coupling reactions. Our results demonstrate the critical role that charge-transfer complexation can play in determining the rates and products of photocatalytic reactions.

Original languageEnglish (US)
Pages (from-to)5911-5917
Number of pages7
Issue number14
StatePublished - Jul 6 2004

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry


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