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

Journal Article · Thu Feb 25 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b01020· OSTI ID:1254151

Hoffeditz, William L.; Katz, Michael J.; Deria, Pravas; Cutsail, George E.; Pellin, Michael J.; Farha, Omar K.; Hupp, Joseph T.

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.

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