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Title: Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells

Abstract

Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO2 solar cell. Here, we report the synthesis, spectral, and electrochemical properties of the sensitizers. Despite slow recombination of photoinjected electrons with oxidized porphyrins, photocurrents are low because of low injection yields and slow electron self-exchange between oxidized porphyrins. As a result, the free-base porphyrins are stable under conditions of water photoelectrolysis and in some cases photovoltages in excess of 1 V are observed.

Authors:
 [1];  [2];  [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [3]
+ Show Author Affiliations
  1. Departments of aChemistry and
  2. Department of Chemistry and Biochemistry and Center for Bio-Inspired Solar Fuel Production, Arizona State University, Tempe, AZ 85287
  3. Departments of aChemistry and, Biochemistry and Molecular Biology, Pennsylvania State University, University Park, PA 16802, and
Publication Date:
Research Org.:
Arizona State Univ., Tempe, AZ (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Solar Fuel Production (BISfuel)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235499
Alternate Identifier(s):
OSTI ID: 1348410
Grant/Contract Number:  
FG02-07ER15911; SC0001016; DGE1255832; ECS-0335765
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 6; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; artificial photosynthesis; metal-free porphyrins; photoelectrochemical; visible light; water-splitting

Citation Formats

Swierk, John R., Méndez-Hernández, Dalvin D., McCool, Nicholas S., Liddell, Paul, Terazono, Yuichi, Pahk, Ian, Tomlin, John J., Oster, Nolan V., Moore, Thomas A., Moore, Ana L., Gust, Devens, and Mallouk, Thomas E. Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells. United States: N. p., 2015. Web. doi:10.1073/pnas.1414901112.
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Swierk, John R., Méndez-Hernández, Dalvin D., McCool, Nicholas S., Liddell, Paul, Terazono, Yuichi, Pahk, Ian, Tomlin, John J., Oster, Nolan V., Moore, Thomas A., Moore, Ana L., Gust, Devens, & Mallouk, Thomas E. Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells. United States. https://doi.org/10.1073/pnas.1414901112
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Swierk, John R., Méndez-Hernández, Dalvin D., McCool, Nicholas S., Liddell, Paul, Terazono, Yuichi, Pahk, Ian, Tomlin, John J., Oster, Nolan V., Moore, Thomas A., Moore, Ana L., Gust, Devens, and Mallouk, Thomas E. Mon . "Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells". United States. https://doi.org/10.1073/pnas.1414901112.
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@article{osti_1235499,
title = {Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells},
author = {Swierk, John R. and Méndez-Hernández, Dalvin D. and McCool, Nicholas S. and Liddell, Paul and Terazono, Yuichi and Pahk, Ian and Tomlin, John J. and Oster, Nolan V. and Moore, Thomas A. and Moore, Ana L. and Gust, Devens and Mallouk, Thomas E.},
abstractNote = {Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO2 solar cell. Here, we report the synthesis, spectral, and electrochemical properties of the sensitizers. Despite slow recombination of photoinjected electrons with oxidized porphyrins, photocurrents are low because of low injection yields and slow electron self-exchange between oxidized porphyrins. As a result, the free-base porphyrins are stable under conditions of water photoelectrolysis and in some cases photovoltages in excess of 1 V are observed.},
doi = {10.1073/pnas.1414901112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 112,
place = {United States},
year = {Mon Jan 12 00:00:00 EST 2015},
month = {Mon Jan 12 00:00:00 EST 2015}
}
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https://doi.org/10.1073/pnas.1414901112
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