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The Cortinarius Fungi Dyes As Sensitizers in Dye-Sensitized Solar Cells

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The Cortinarius Fungi Dyes As Sensitizers in Dye-Sensitized Solar Cells Hindawi Publishing Corporation International Journal of Photoenergy Volume 2015, Article ID 653740, 6 pages http://dx.doi.org/10.1155/2015/653740 Research Article The Cortinarius Fungi Dyes as Sensitizers in Dye-Sensitized Solar Cells Maciej Zalas, BBahej Gierczyk, Hubert Bogacki, and Grzegorz Schroeder Faculty of Chemistry, Adam Mickiewicz University in Poznan,´ Umultowska 89B, 61-614 Poznan,´ Poland Correspondence should be addressed to Maciej Zalas; [email protected] Received 11 November 2014; Revised 10 December 2014; Accepted 11 December 2014 Academic Editor: Rajaram S. Mane Copyright © 2015 Maciej Zalas et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The dye-sensitized solar cells have been for the first time prepared using Cortinarius fungi extracts as a source of sensitizing dyes. The seven species of Cortinarius group,collectedintheEastPoland,havebeenusedtoobtaincrudeextractsofnaturaldyesused as sensitizing solutions to prepare DSSCs working electrodes. Extracts and sensitized electrodes have been well characterized by UV-Vis spectroscopy measurements. The device sensitized by Cortinarius sanguineus extract has been found the most active in = 0.64 = 65.9 = 1.79 2 photon-to-current conversion process with efficiency %, fill factor FF %, photocurrent density SC mA/cm , = 541 and photovoltage OC mV. 1. Introduction the mesoporous electrode and external circuit into the counter electrode. Now electron reduces the oxidized form Since the first presentation of efficient device by O’Regan of the redox couple in the electrolyte and, as the last step, and Graetzel in 1991 [1], the dye sensitized solar cells (DSSC) the reaction between the reduced form of the redox mediator have become a widely studied inexpensive alternative to and the oxidized dye molecule occurs; thereupon the ground silicon solar cells [2]. The main advantage of such devices is state of the dye molecule and oxidized form of the redox relatively uncomplicated construction and ability to obtain couplearerestoredandtheDSSCworkingcycleisclosed[2– high efficiencies with no use of expensive materials and Hi- 4]. In the ideal system the whole process takes place without Purity Chemicals. Typical DSSC is built with two sheets of consumption or permanent transformation of any chemical transparent conductive oxide (TCO) coated glass, one of species and theoretically it can occur as long as illumination which, the so-called working electrode, is covered with the is present. mesoporous electrode, mostly made of nanocrystalline TiO2, Dyes used in DSSC devices belong to various chemical sensitized with a dye (mostly ruthenium complexes). The classes. Most intensively studied are synthetic pigments, espe- second TCO glass sheet, the so-called counter electrode, is cially polypyridine complexes of ruthenium [5, 6], but also covered by a thin layer of platinum. These two electrodes are metal-free molecules are used for this purpose (e.g., oligoth- arranged in a sandwich cell and the space between them is iophenes, coumarins, squaric acid derivatives, triarylamine − − filled with a liquid electrolyte containing I /I3 redox pair pigments, etc.) [7]. As the synthesis of these compounds solution in organic solvent(s) [2]. The principle mechanism requires multistep reaction, their preparation is expensive of the DSSC working cycle is straightforward and may be and far from the principles of environmental-friendly green described with five steps of electron movement. The first chemistry. Interesting alternatives to synthetic dyes used stepistheexcitationofanelectronfromthegroundtothe in DSSC are natural pigments [8–13]. Many compounds, excited state of the dye molecule by a photon of incident light. isolated from plants and animals, meet the requirements of Next, the excited electron is injected from the dye molecule pigments useful for solar cells: they contain chromophores into the conducting band of the mesoporous semiconduct- absorbing the light in a wide wavelength range; the hydroxyl ing electrode; afterwards the electron is transported across or carboxyl groups of these pigments are able to bind 2 International Journal of Photoenergy Table 1: Cortinarius fungiusedforDSSCspreparation. Sample Scientific name Locality Habitat Near Osowiec-Twierdza village (NE Mixed forest (Betula pendula, Betula Css1 Cortinarius semisanguineus Poland) pubescens, Pinus sylvestris) Mixed forest (Pinus sylvestris, Quercus Cs1 Cortinarius sanguineus Near Białowieza˙ village (NE Poland) robur) Mixed forest (Pinus sylvestris, Quercus Csp1 Cortinarius sp. (sect. Telamonia) Near Białowieza˙ village (NE Poland) robur) Coniferous forest (Picea abies, Pinus Csp2 Cortinarius sp. (sect. Dermocybe) Near Czerlonka village (NE Poland) sylvestris) Coniferous forest (Picea abies, Pinus Cc1 Cortinarius croceus Near Czerlonka village (NE Poland) sylvestris) Mixed forest (Pinus sylvestris, Quercus Css2 Cortinarius semisanguineus Near Czerlonka village (NE Poland) robur) to TiO2 surface and they are usually quite stable under In this work a series of DSSCs sensitized by crude extracts sun irradiation. Natural dyes are very attractive for DSSC of various fungi from the genus Cortinarius was obtained application as they are low-cost, available in large quantities, and characterized. The photocurrent characteristics of the and sustainable. There are two approaches to the use of cells and spectroscopic data of the extracted dyes were natural colorants in DSSC. According to the first, a single determined. isolated and purified compound (or compounds group) is used as a sensitizer, while the second one involves the use 2. Experimental of a crude extract for sensitization of the TiO2 layer. Various natural pigment classes are recognized as active components 2.1. Preparation of Dyes Extracts. The fungi basidiocarps for photosensitization of DSSCs. The most important are werecollectedinautumn2013.Fruitingbodieswereplaced chlorophylls, carotenoids, and anthocyanins. The highest in electric fruit dryer within 5 h after picking; the drying efficiencies ( = 3.7–4.2) were detected for the systems con- temperaturewaslowerthan313K.Driedmaterialwasstored taining a semisynthetic chlorophyll derivative and carotenoid at room temperature in the dark. Then 1 g of finely crushed, (e.g., neoxanthin or -carotene) [14].Inthesecondapproach, dried basidiocarps was mixed with 20 mL of methanol. So the highest efficiencies of photosensitization were observed obtained mixtures were left at 278 K in the dark. After 24 h the for the extracts from betalains-containing beet root (Beta solids were filtered off using 0.45 m PTFE syringe filters, and vulgaris; = 2.2–2.7)[15], azaphilones-producing ang- the obtained extracts were used to sensitize titania electrodes khak rice mold (Monascus purpureus, = 2.3)[16], and for DSSCs. The origin of the fungi used in this study is given chalcones-containing flowers of Flame of the Forest tree in Table 1. (Butea monosperma, = 1.8)[17]. Except for Monascus purpureus,nootherfungihavebeenusedasasourceof 2.2. DSSCs Preparation and Characterization. All chemicals DSSCs sensitizers; in particular no species belonging to used were of analytical grade and were used as received macromycetes have been studied for this purpose. without any additional purification. The procedure used for The genus Cortinarius (Agaricales, Basidiomycota) is a preparation of the titania electrodes was similar to those large and very diverse group of fungi. The species belonging described elsewhere [26] and was as follows: 3 mL titanium to genus Cortinarius form agaricoid, medium to large, inten- tetraisopropoxide (Aldrich) was added to 13.5 mL of ethylene sively colored basidiocarps. Peculiar group of the Cortinarius glycol (Chempur) magnetically stirred at 333 K. The mixture, species are the taxa belonging to the section Dermocybe after addition 12.6 g of citric acid monohydrate (POCh), was (commonly known as skin-heads). They produce medium- heated under stirring at 363 K, until clear. The transparent size fruiting bodies with intense, bright colors of vari- solobtainedwasmixedwith5.6gP25TiO2 (Degussa) by ous shades of red, orange, yellow, and ocher. In Nordic grinding in an agate mortar for 1 hour. The viscous titania countries the extracts from Dermocybe representatives are paste obtained was spread on fluorine doped tin oxide (FTO) traditionally used for dying textiles, especially wool [18]. The conductive glass substrate (Solaronix) using “doctor blade” pigments isolated from these fungi belong to anthraquinones technique and sintered in air at 723 K for 2 hours. To prepare (emodin, dermorubin, dermocybin), xanthones (dermoxan- the working electrodes for DSSCs, titania electrodes were thone), pyranonaphthoquinones (cardinalin), and chrysones immersed in Cortinarius extracts at 278 K overnight. After (dermochrysone) [19–23]. Although quinones and quinone- dye adsorption, the electrodes were washed with absolute related compounds contain groups that allow their binding ethanol and dried in hot air stream. Platinum film coated FTO to TiO2 surface, they have been rarely studied as natural was used as a counter electrode. A typical cell was assembled sensitizers of DSSCs. The only example is the application using a 25 m thick, hot-melted, ionomeric foil (Solaronix) of henna extract (Lawsonia inermis), containing lawsone, a as a sealant and a spacer
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