Bioinspired high-potential porphyrin photoanodes

Gary F. Moore, Steven J. Konezny, Hee Eun Song, Rebecca L. Milot, James D. Blakemore, Minjoo L. Lee, Victor S. Batista, Charles A. Schmuttenmaer, Robert H. Crabtree, Gary W Brudvig

Research output: Contribution to journalArticle

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Abstract

We report a selection of high-potential porphyrin photoanodes (HPPPs) for use in photoelectrochemical cells (PECs). The anodes consist of bispentafluorophenyl free-base and metallo-porphyrin sensitizers bearing anchoring groups for attachment to metal-oxide surfaces including TiO 2 and SnO 2 nanoparticles. The term "high potential" refers to the relatively large and positive value of the electrochemical reduction potential for the bispentafluorophenyl porphyrin radical cation (P ̇+ + e - → P) as compared with more conventional nonfluorinated analogues. Photoelectrochemical measurements demonstrate the sensitizers used in these HPPPs extend the absorption of the bare anode well into the visible region. Terahertz spectroscopic studies show the photoexcited dyes are capable of injecting electrons into the conduction band of an underlying metal-oxide with appropriate energetics. The reduction potentials of the resulting photogenerated porphyrin radical cations are relatively high (ranging from ∼1.35 to 1.65 V vs NHE depending on the sensitizer). This is demonstrated by the ability of dye-sensitized solar cells, containing our HPPPs, to use the Br 3 -/Br - redox couple as a regenerative electron mediator with superior performance in comparison to results obtained using the lower-potential I 3 -/I - relay. Computational modeling of the structures and equivalent circuits assists in a molecular-based understanding of these systems. Further, the oxidation power of the porphyrin radical cations generated in these bioinspired constructs is similar to that found in the reaction centers of their natural counterpart (photosystem II); thus, HPPPs are promising as components in artificial systems for photochemical water spitting applications.

Original languageEnglish
Pages (from-to)4892-4902
Number of pages11
JournalJournal of Physical Chemistry C
Volume116
Issue number7
DOIs
Publication statusPublished - Feb 23 2012

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Porphyrins
porphyrins
Cations
Positive ions
cations
Oxides
metal oxides
Anodes
anodes
Bearings (structural)
dyes
Metals
Photoelectrochemical cells
Photosystem II Protein Complex
Electrons
relay
Conduction bands
equivalent circuits
Equivalent circuits
attachment

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Moore, G. F., Konezny, S. J., Song, H. E., Milot, R. L., Blakemore, J. D., Lee, M. L., ... Brudvig, G. W. (2012). Bioinspired high-potential porphyrin photoanodes. Journal of Physical Chemistry C, 116(7), 4892-4902. https://doi.org/10.1021/jp210096m

Bioinspired high-potential porphyrin photoanodes. / Moore, Gary F.; Konezny, Steven J.; Song, Hee Eun; Milot, Rebecca L.; Blakemore, James D.; Lee, Minjoo L.; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

In: Journal of Physical Chemistry C, Vol. 116, No. 7, 23.02.2012, p. 4892-4902.

Research output: Contribution to journalArticle

Moore, GF, Konezny, SJ, Song, HE, Milot, RL, Blakemore, JD, Lee, ML, Batista, VS, Schmuttenmaer, CA, Crabtree, RH & Brudvig, GW 2012, 'Bioinspired high-potential porphyrin photoanodes', Journal of Physical Chemistry C, vol. 116, no. 7, pp. 4892-4902. https://doi.org/10.1021/jp210096m
Moore GF, Konezny SJ, Song HE, Milot RL, Blakemore JD, Lee ML et al. Bioinspired high-potential porphyrin photoanodes. Journal of Physical Chemistry C. 2012 Feb 23;116(7):4892-4902. https://doi.org/10.1021/jp210096m
Moore, Gary F. ; Konezny, Steven J. ; Song, Hee Eun ; Milot, Rebecca L. ; Blakemore, James D. ; Lee, Minjoo L. ; Batista, Victor S. ; Schmuttenmaer, Charles A. ; Crabtree, Robert H. ; Brudvig, Gary W. / Bioinspired high-potential porphyrin photoanodes. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 7. pp. 4892-4902.
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