Thiophene-based phenothiazines for dye-sensitized solar cells and photocatalytic H2 production: enhanced stability properties

Norberto Manfredi^a, Riccardo Ruffo^a, Alessandro Abbotto^a, Bianca Cecconi^a, Tiziano Montini^b, Paolo Fornasiero^b

^aDepartment of Chemical and Pharmaceutical Sciences ICCOM-CNR, Consortium INSTM Trieste Research Unit University of Trieste, Via L. Giorgieri 1, Trieste, 34127, Italy

International Conference on Hybrid and Organic Photovoltaics
Proceedings of International Conference on Hybrid and Organic Photovoltaics 2015 (HOPV15)

Roma, Italy, 2015 May 11th - 13th

Organizer: Filippo De Angelis

Poster, Bianca Cecconi, 163
Publication date: 5th February 2015

In recent years hydrogen production from renewable sources has attracted increasing interest of many research groups. Indeed hydrogen could be a good candidate as a solar fuel since it has no carbon footprint when burst and can be obtained from water through molecular splitting processes. Splitting of water molecules is an energy demanding process and solar radiation could provide such request. Inspired by DSSC technology, an analogous mechanism can be envisaged for water splitting, as it is illustrated in Figure 1a. We focused our attention on dyes as the first interface of the device towards solar radiation, in particular on organic metal-free sensitizers, since they have been scantly investigated so far for dye-sensitized hydrogen production. We selected the dye-architecture of the multi-branched multi-anchoring D(-π-A)₂ geometry, firstly introduced by us a few years ago and now widely used in the DSSC field.[1]^,>[2] Here we present the effect of different conjugated π-spacer in water splitting and DSSC performances. We tested a series of D(-π-A)₂ dyes where D is a phenothiazine donor core, A is the acceptor-anchoring cyano-acrylic group and π varies as different thiophene derivatives (Figure 1b). Design of the π-spacer afforded significant enhancement of optical properties, up to a four-fold increase of the molar absorptivity and red-shifting. Compared to the reference dye with no π-spacer,[3] the new sensitizers showed higher stability in water improved long-term hydrogen production upon irradiation.
Figure 1: a) Dye-sensitized H2 production; b) Sensitizers developed in this work.
[1]Abbotto, A.; Manfredi, N.; Marinzi, C.; De Angelis, F.; Mosconi, E.; Yum, J.-H.; Xianxi, Z., Nazeeruddin, M. K.; Grätzel, M. Di-Branched Di-Anchoring Organic Dyes for Dye-Sensitized Solar Cells. Energy Environ. Sci. 2009, 2, 1094-1101. [2] Review: Manfredi, N.; Cecconi, B.; Abbotto, A. Multi-Branched Multi-Anchoring Metal-Free Dyes for Dye-Sensitized Solar Cells. Eur. J. Org. Chem., 2014, 32, 7069-7086; Leandri, V.; Ruffo, R.; Trifiletti, V.; Abbotto, A. Asymmetric Tribranched Dyes: An Intramolecular Cosensitization Approach for Dye-Sensitized Solar Cells. Eur. J. Org. Chem. 2013, 6793-6801; Abbotto, A.; Leandri, V.; Manfredi, N.; De Angelis, F.; Pastore, M.; Yum, J.-H.; Nazeeruddin, M. K.; Grätzel, M. Bis-Donor–Bis-Acceptor Tribranched Organic Sensitizers for Dye-Sensitized Solar Cells. Eur. J. Org. Chem. 2011, 6195-6205. [3] Lee, J.; Kwak, J.; Ko, J. C.; Park, J. H.; Ko, J. H.; Park, N.; Kim, E.; Ryu, D. H.; Ahn, T. K.; Lee, Son, S. U. Phenothiazine-Based Organic Dyes with Two Anchoring Groups on TiO2 for Highly Efficient Visible Light-Induced Water Splitting Chem. Commun. 2012, 48, 11431-11433.

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