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Title: High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications

Here, we report CF 3-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. Furthermore, by using (CF 3) 2C 6H 3 instead of C 6F 5 substituents at the meso positions, we obtain the desired high potentials while avoiding the sensitivity of C 6F 5 substituents to nucleophilic substitution, a process that limits the types of synthetic reactions that can be used. Both the number of CF 3 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 SnO 2 and TiO 2 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 also found that both free-base and metallated porphyrins inject into SnO 2, and that recombination is slower for the latter case. Our findings demonstrate that (CF 3) 2C 6H 3-substituted porphyrins are promising photosensitizers for use in WS-DSPECs.
Authors:
 [1] ;  [1] ;  [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Sciences Inst.
Publication Date:
Grant/Contract Number:
FG02-07ER15909
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 51; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Yale Univ., New Haven, CT (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; interfacial electron transfer; photosensitizers; transient absorption; terahertz spectroscopy; trifluoromethylphenyl; density functional theory
OSTI Identifier:
1334233

Jiang, Jianbing, Swierk, John R., Materna, Kelly L., Hedström, Svante, Lee, Shin Hee, Crabtree, Robert H., Schmuttenmaer, Charles A., Batista, Victor S., and Brudvig, Gary W.. High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications. United States: N. p., Web. doi: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 SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications. United States. doi: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., and Brudvig, Gary W.. 2016. "High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications". United States. doi:10.1021/acs.jpcc.6b10350. https://www.osti.gov/servlets/purl/1334233.
@article{osti_1334233,
title = {High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications},
author = {Jiang, Jianbing and Swierk, John R. and Materna, Kelly L. and Hedström, Svante and Lee, Shin Hee and Crabtree, Robert H. and Schmuttenmaer, Charles A. and Batista, Victor S. and Brudvig, Gary W.},
abstractNote = {Here, 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. Furthermore, 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 also found that both free-base and metallated porphyrins inject into SnO2, and that recombination is slower for the latter case. Our findings demonstrate that (CF3)2C6H3-substituted porphyrins are promising photosensitizers for use in WS-DSPECs.},
doi = {10.1021/acs.jpcc.6b10350},
journal = {Journal of Physical Chemistry. C},
number = 51,
volume = 120,
place = {United States},
year = {2016},
month = {12}
}