Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes

Laura I. Hernández, Robert Godin, Jesse J. Bergkamp, Manuel J. Llansola Portolés, Benjamin D. Sherman, John Tomlin, Gerdenis Kodis, Dalvin D. Méndez-Hernández, Sonia Bertolotti, Carlos A. Chesta, Ernesto Mariño-Ochoa, Ana Moore, Thomas Moore, Gonzalo Cosa, Rodrigo E. Palacios

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

We report on the photosensitization of titanium dioxide nanoparticles (TiO2 NPs) synthesized inside AOT (bis(2-ethylhexyl) sulfosuccinate sodium salt) reverse micelles following photoexcitation of perylene derivatives with dicarboxylate anchoring groups. The dyes, 1,7-dibromoperylene-3,4,9,10- tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2), and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10- tetracarboxy dianhydride (3), have considerably different driving forces for photoinduced electron injection into the TiO2 conduction band, as estimated by electrochemical measurements and quantum mechanical calculations. Fluorescence anisotropy measurements indicate that dyes 1 and 2 are preferentially solubilized in the micellar structure, creating a relatively large local concentration that favors the attachment of the dye to the TiO 2 surface. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time for 1 and 2. Photoinduced electron transfer from the singlet excited state of 1 and 2 to the TiO2 conduction band (CB) is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2 semiconductor. Steady state and transient spectroscopy indicate that dye 3 does not bind to the TiO2 NPs and does not photosensitize the semiconductor. This observation was rationalized as a consequence of the bulky t-butylphenyloxy groups which create a strong steric impediment for deep access of the dye within the micelle structure to reach the semiconductor oxide surface.

Original languageEnglish (US)
Pages (from-to)4568-4581
Number of pages14
JournalJournal of Physical Chemistry B
Volume117
Issue number16
DOIs
StatePublished - Apr 25 2013

Fingerprint

Micelles
micelles
Coloring Agents
Dyes
dyes
Nanoparticles
nanoparticles
Conduction bands
conduction bands
Dioctyl Sulfosuccinic Acid
Perylene
Semiconductor materials
Electron injection
Electrons
Photoexcitation
photoexcitation
Excited states
titanium oxides
Titanium dioxide
attachment

ASJC Scopus subject areas

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

Cite this

Hernández, L. I., Godin, R., Bergkamp, J. J., Llansola Portolés, M. J., Sherman, B. D., Tomlin, J., ... Palacios, R. E. (2013). Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes. Journal of Physical Chemistry B, 117(16), 4568-4581. https://doi.org/10.1021/jp3086792

Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes. / Hernández, Laura I.; Godin, Robert; Bergkamp, Jesse J.; Llansola Portolés, Manuel J.; Sherman, Benjamin D.; Tomlin, John; Kodis, Gerdenis; Méndez-Hernández, Dalvin D.; Bertolotti, Sonia; Chesta, Carlos A.; Mariño-Ochoa, Ernesto; Moore, Ana; Moore, Thomas; Cosa, Gonzalo; Palacios, Rodrigo E.

In: Journal of Physical Chemistry B, Vol. 117, No. 16, 25.04.2013, p. 4568-4581.

Research output: Contribution to journalArticle

Hernández, LI, Godin, R, Bergkamp, JJ, Llansola Portolés, MJ, Sherman, BD, Tomlin, J, Kodis, G, Méndez-Hernández, DD, Bertolotti, S, Chesta, CA, Mariño-Ochoa, E, Moore, A, Moore, T, Cosa, G & Palacios, RE 2013, 'Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes', Journal of Physical Chemistry B, vol. 117, no. 16, pp. 4568-4581. https://doi.org/10.1021/jp3086792
Hernández LI, Godin R, Bergkamp JJ, Llansola Portolés MJ, Sherman BD, Tomlin J et al. Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes. Journal of Physical Chemistry B. 2013 Apr 25;117(16):4568-4581. https://doi.org/10.1021/jp3086792
Hernández, Laura I. ; Godin, Robert ; Bergkamp, Jesse J. ; Llansola Portolés, Manuel J. ; Sherman, Benjamin D. ; Tomlin, John ; Kodis, Gerdenis ; Méndez-Hernández, Dalvin D. ; Bertolotti, Sonia ; Chesta, Carlos A. ; Mariño-Ochoa, Ernesto ; Moore, Ana ; Moore, Thomas ; Cosa, Gonzalo ; Palacios, Rodrigo E. / Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes. In: Journal of Physical Chemistry B. 2013 ; Vol. 117, No. 16. pp. 4568-4581.
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