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Towards Sustainable H 2 Production: Rational Design of Hydrophobic Triphenylamine‐based Dyes for Sensitized Ethanol Photoreforming
Author(s) -
Dessì Alessio,
Monai Matteo,
Bessi Matteo,
Montini Tiziano,
Calamante Massimo,
Mordini Alessandro,
Reginato Gianna,
Trono Cosimo,
Fornasiero Paolo,
Zani Lorenzo
Publication year - 2018
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201701707
Subject(s) - triethanolamine , triphenylamine , chemistry , photochemistry , electron donor , moiety , photocatalysis , alkyl , electron acceptor , combinatorial chemistry , organic chemistry , catalysis , analytical chemistry (journal)
Donor–acceptor dyes are a well‐established class of photosensitizers, used to enhance visible‐light harvesting in solar cells and in direct photocatalytic reactions, such as H 2 production by photoreforming of sacrificial electron donors (SEDs). Amines—typically triethanolamine (TEOA)—are commonly employed as SEDs in such reactions. Dye‐sensitized photoreforming of more sustainable, biomass‐derived alcohols, on the other hand, was only recently reported by using methanol as the electron donor. In this work, several rationally designed donor–acceptor dyes were used as sensitizers in H 2 photocatalytic production, comparing the efficiency of TEOA and EtOH as SEDs. In particular, the effect of hydrophobic chains in the spacer and/or the donor unit of the dyes was systematically studied. The H 2 production rates were higher when TEOA was used as SED, whereas the activity trends depended on the SED used. The best performance was obtained with TEOA by using a sensitizer with just one bulky hydrophobic moiety, propylenedioxythiophene, placed on the spacer unit. In the case of EtOH, the best‐performing sensitizers were the ones featuring a thiazolo[5,4‐ d ]thiazole internal unit, needed for enhancing light harvesting, and carrying alkyl chains on both the donor part and the spacer unit. The results are discussed in terms of reaction mechanism, interaction with the SED, and structural/electrochemical properties of the sensitizers.