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Title: One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.

Abstract

Dye-sensitized solar cells (DSCs) are an established alternative photovoltaic technology that offers numerous potential advantages in solar energy applications. However, this technology has been limited by the availability of molecular redox couples that are both noncorrosive/nontoxic and do not diminish the performance of the device. In an effort to overcome these shortcomings, a copper-containing redox shuttle derived from 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (PDTO) ligand and the common DSC additive 4-tert-butylpyridine (TBP) was investigated. Electrochemical measurements, single-crystal X-ray diffraction, and absorption and electron paramagnetic resonance spectroscopies reveal that, upon removal of one metal-centered electron, PDTO-enshrouded copper ions completely shed the tetradentate PDTO ligand and replace it with four or more TBP ligands. Thus, the Cu(I) and Cu(II) forms of the electron shuttle have completely different coordination spheres and are characterized by widely differing Cu(II/I) formal potentials and reactivities for forward versus reverse electron transfer. Notably, the coordination-sphere replacement process is fully reversed upon converting Cu(II) back to Cu(I). In cells featuring an adsorbed organic dye and a nano- and mesoparticulate, TiO2-based, photoelectrode, the dual species redox shuttle system engenders performance superior to that obtained with shuttles based on the (II/I) forms of either of the coordination complexes in isolation.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division; National Institutes of Health (NIH); Northwestern University
OSTI Identifier:
1254151
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 7; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Hoffeditz, William L., Katz, Michael J., Deria, Pravas, Cutsail, George E., Pellin, Michael J., Farha, Omar K., and Hupp, Joseph T. One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b01020.
Hoffeditz, William L., Katz, Michael J., Deria, Pravas, Cutsail, George E., Pellin, Michael J., Farha, Omar K., & Hupp, Joseph T. One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.. United States. doi:10.1021/acs.jpcc.6b01020.
Hoffeditz, William L., Katz, Michael J., Deria, Pravas, Cutsail, George E., Pellin, Michael J., Farha, Omar K., and Hupp, Joseph T. Thu . "One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.". United States. doi:10.1021/acs.jpcc.6b01020.
@article{osti_1254151,
title = {One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.},
author = {Hoffeditz, William L. and Katz, Michael J. and Deria, Pravas and Cutsail, George E. and Pellin, Michael J. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Dye-sensitized solar cells (DSCs) are an established alternative photovoltaic technology that offers numerous potential advantages in solar energy applications. However, this technology has been limited by the availability of molecular redox couples that are both noncorrosive/nontoxic and do not diminish the performance of the device. In an effort to overcome these shortcomings, a copper-containing redox shuttle derived from 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (PDTO) ligand and the common DSC additive 4-tert-butylpyridine (TBP) was investigated. Electrochemical measurements, single-crystal X-ray diffraction, and absorption and electron paramagnetic resonance spectroscopies reveal that, upon removal of one metal-centered electron, PDTO-enshrouded copper ions completely shed the tetradentate PDTO ligand and replace it with four or more TBP ligands. Thus, the Cu(I) and Cu(II) forms of the electron shuttle have completely different coordination spheres and are characterized by widely differing Cu(II/I) formal potentials and reactivities for forward versus reverse electron transfer. Notably, the coordination-sphere replacement process is fully reversed upon converting Cu(II) back to Cu(I). In cells featuring an adsorbed organic dye and a nano- and mesoparticulate, TiO2-based, photoelectrode, the dual species redox shuttle system engenders performance superior to that obtained with shuttles based on the (II/I) forms of either of the coordination complexes in isolation.},
doi = {10.1021/acs.jpcc.6b01020},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 7,
volume = 120,
place = {United States},
year = {2016},
month = {2}
}