title: Oxidovanadium(IV/V) complexes as new redox mediators in dye-sensitized solar cells: a combined experimental and theoretical study.
abstract: Corrosiveness is one of the main drawbacks of using the iodide/triiodide redox couple in dye-sensitized solar cells (DSSCs). Alternative redox couples including transition metal complexes have been investigated where surprisingly high efficiencies for the conversion of solar to electrical energy have been achieved. In this paper, we examined the development of a DSSC using an electrolyte based on square pyramidal oxidovanadium(IV/V) complexes. The oxidovanadium(IV) complex (Ph4P)2[V(IV)O(hybeb)] was combined with its oxidized analogue (Ph4P)[V(V)O(hybeb)] {where hybeb(4-) is the tetradentate diamidodiphenolate ligand [1-(2-hydroxybenzamido)-2-(2-pyridinecarboxamido)benzenato}and applied as a redox couple in the electrolyte of DSSCs. The complexes exhibit large electron exchange and transfer rates, which are evident from electron paramagnetic resonance spectroscopy and electrochemistry, rendering the oxidovanadium(IV/V) compounds suitable for redox mediators in DSSCs. The very large self-exchange rate constant offered an insight into the mechanism of the exchange reaction most likely mediated through an outer-sphere exchange mechanism. The [V(IV)O(hybeb)](2-)/[V(V)O(hybeb)](-) redox potential and the energy of highest occupied molecular orbital (HOMO) of the sensitizing dye N719 and the HOMO of [V(IV)O(hybeb)](2-) were calculated by means of density functional theory electronic structure calculation methods. The complexes were applied as a new redox mediator in DSSCs, while the cell performance was studied in terms of the concentration of the reduced and oxidized form of the complexes. These studies were performed with the commercial Ru-based sensitizer N719 absorbed on a TiO2 semiconducting film in the DSSC. Maximum energy conversion efficiencies of 2% at simulated solar light (AM 1.5; 1000 W m(-2)) with an open circuit voltage of 660 mV, a short-circuit current of 5.2 mA cm(-2), and a fill factor of 0.58 were recorded without the presence of any additives in the electrolyte.
authors.affiliation: †Nanotechnology and Advanced Materials Laboratory, Electrical Engineering Department, Technological-Educational Institute of Western Greece, GR-26334 Patras, Greece.|∥Department of Physics, University of Patras, GR-26500 Patras, Greece.
authors.forename: Andigoni
authors.initials: A
authors.lastname: Apostolopoulou
authors.affiliation: ‡Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus.
authors.forename: Manolis
authors.initials: M
authors.lastname: Vlasiou
authors.forename: Petros A
authors.initials: PA
authors.lastname: Tziouris
authors.forename: Constantinos
authors.initials: C
authors.lastname: Tsiafoulis
authors.forename: Athanassios C
authors.initials: AC
authors.lastname: Tsipis
authors.affiliation: ⊥Department of Chemistry, University of Hamburg, D-20146 Hamburg, Germany.
authors.forename: Dieter
authors.initials: D
authors.lastname: Rehder
authors.forename: Themistoklis A
authors.initials: TA
authors.lastname: Kabanos
authors.affiliation: ‡Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus.
authors.forename: Anastasios D
authors.initials: AD
authors.lastname: Keramidas
authors.affiliation: †Nanotechnology and Advanced Materials Laboratory, Electrical Engineering Department, Technological-Educational Institute of Western Greece, GR-26334 Patras, Greece.
authors.forename: Elias
authors.initials: E
authors.lastname: Stathatos
mesh_terms: D004396:Coloring Agents / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011789:Quantum Theory; D012993:Solar Energy; D014638:Vanadates / Q000737:chemistry*
chemical_list: D004396:Coloring Agents; D056831:Coordination Complexes; D014638:Vanadates