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Burschka, Julian,Brault, Vincent,Ahmad, Shahzada,Breau, Livain,Nazeeruddin, Mohammad K.,Marsan, Benoî,t,Zakeeruddin, Shaik M.,Grä,tzel, Michael The Royal Society of Chemistry 2012 ENERGY AND ENVIRONMENTAL SCIENCE Vol.5 No.3
<P>Strong scientific interests focus on the investigation of iodine-free redox couples for their application in dye-sensitized solar cells (DSCs). Recently, a disulfide/thiolate-based redox electrolyte has been proposed as a valuable alternative to the conventional I<SUB>3</SUB><SUP>−</SUP>/I<SUP>−</SUP> system due to its transparent and non-corrosive nature. In the work presented herein, we systematically studied the influence of different counter electrode materials on the photovoltaic performance of DSCs employing this promising organic redox electrolyte. Our investigations focused on understanding the importance of electrocatalytic activity and surface area of the electroactive material on the counter electrode, comparing the conventional platinum to cobalt sulfide (CoS) and poly(3,4-ethylenedioxythiophene) (PEDOT). Electrochemical Impedance Spectroscopy has been used to study in detail the interfacial charge transfer reaction at the counter electrode. By using a high surface area PEDOT-based counter electrode, we finally achieved an unprecedented power conversion efficiency of 7.9% under simulated AM1.5G solar irradiation (100 mW cm<SUP>−2</SUP>) which, to the best of our knowledge, represents the highest efficiency that has so far been reported for an organic redox couple.</P> <P>Graphic Abstract</P><P>Investigation of platinum-free electrocatalysts for disulfide-to-thiolate reduction in dye-sensitized solar cells leading to a new record efficiency of 7.9%. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2ee03005e'> </P>
Photosensitizing properties of chlorins in solution and in membrane-mimicking systems
Mojzisova, Halina,Bonneau, Stephanie,Maillard, Philippe,Berg, Kristian,Brault, Daniel Korean Society of Photoscience 2009 Photochemical & photobiological sciences Vol.8 No.6
The photosensitizing properties of three chlorins, meso-tetra(3-hydroxyphenyl)chlorin (m-THPC), chlorin e6 (Ce6) and meso-tetraphenylchlorin substituted by two adjacent sulfonated groups ($TPCS_{2a}$) are compared in solution and when incorporated in dioleoyl-sn-phosphatidylcholine (DOPC) liposomes. In solution, the three chlorins possess a similar efficacy to generate singlet oxygen (quantum yield ~0.65). The formation of conjugated dienes was used to determine their ability to induce the peroxidation of methyl linoleate as a target of singlet oxygen. In ethanol solution, the apparent quantum yield for this process is the same for the three chlorins and its value agrees with that expected from the known rates for the decay of singlet oxygen and its reaction with methyl linoleate. When incorporated in liposomes, the order of efficacy is m-THPC > $TPCS_{2a}$ > Ce6. This order is tentatively assigned to the relative embedment of the photosensitizer within the lipidic bilayer, $TPCS_{2a}$ and Ce6 being anchored by their negative chains nearer to the water-lipid interface. The photoinduced permeation of the lipidic bilayer by these chlorins was investigated by measuring the release of carboxyfluorescein entrapped into DOPC liposomes. The charged chlorins, in particular $TPCS_{2a}$, are the most efficient, a result discussed in relation with the technology of photochemical internalization, PCI.