High-Potential Porphyrins Supported on SnO2 and TiO2 Surfaces for Photoelectrochemical Applications

Jianbing Jiang, John R. Swierk, Kelly L. Materna, Svante Hedström, Shin Hee Lee, Robert H. Crabtree, Charles A. Schmuttenmaer, Victor S. Batista, Gary W Brudvig

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

We report CF3-substituted porphyrins and evaluate their use as photosensitizers in water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) by characterizing interfacial electron transfer on metal oxide surfaces. By using (CF3)2C6H3 instead of C6F5 substituents at the meso positions, we obtain the desired high potentials while avoiding the sensitivity of C6F5 substituents to nucleophilic substitution, a process that limits the types of synthetic reactions that can be used. Both the number of CF3 groups and the central metal tune the ground and excited-state potentials. A pair of porphyrins bearing carboxylic acids as anchoring groups were deposited on SnO2 and TiO2 surfaces, and the interfacial charge-injection and charge-recombination kinetics were characterized by using a combination of computational modeling, terahertz measurements, and transient absorption spectroscopy. We find that both free-base and metalated porphyrins inject into SnO2 and that recombination is slower for the latter case. These findings demonstrate that (CF3)2C6H3-substituted porphyrins are promising photosensitizers for use in WS-DSPECs. (Graph Presented).

Original languageEnglish
Pages (from-to)28971-28982
Number of pages12
JournalJournal of Physical Chemistry C
Volume120
Issue number51
DOIs
Publication statusPublished - Dec 29 2016

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Porphyrins
porphyrins
Photoelectrochemical cells
water splitting
Photosensitizing Agents
Photosensitizers
Coloring Agents
Bearings (structural)
Dyes
dyes
Metals
Charge injection
Water
Carboxylic Acids
cells
Absorption spectroscopy
Carboxylic acids
Excited states
carboxylic acids
Oxides

ASJC Scopus subject areas

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

Cite this

High-Potential Porphyrins Supported on SnO2 and TiO2 Surfaces for Photoelectrochemical Applications. / Jiang, Jianbing; Swierk, John R.; Materna, Kelly L.; Hedström, Svante; Lee, Shin Hee; Crabtree, Robert H.; Schmuttenmaer, Charles A.; Batista, Victor S.; Brudvig, Gary W.

In: Journal of Physical Chemistry C, Vol. 120, No. 51, 29.12.2016, p. 28971-28982.

Research output: Contribution to journalArticle

Jiang, J, Swierk, JR, Materna, KL, Hedström, S, Lee, SH, Crabtree, RH, Schmuttenmaer, CA, Batista, VS & Brudvig, GW 2016, 'High-Potential Porphyrins Supported on SnO2 and TiO2 Surfaces for Photoelectrochemical Applications', Journal of Physical Chemistry C, vol. 120, no. 51, pp. 28971-28982. https://doi.org/10.1021/acs.jpcc.6b10350
Jiang, Jianbing ; Swierk, John R. ; Materna, Kelly L. ; Hedström, Svante ; Lee, Shin Hee ; Crabtree, Robert H. ; Schmuttenmaer, Charles A. ; Batista, Victor S. ; Brudvig, Gary W. / High-Potential Porphyrins Supported on SnO2 and TiO2 Surfaces for Photoelectrochemical Applications. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 51. pp. 28971-28982.
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