Dithiafulvalene functionalized diketopyrrolopyrrole based sensitizers for efficient hydrogen production
IR@CMERI: CSIR- Central Mechanical Engineering Research Institute (CMERI), Durgapur
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| Title |
Dithiafulvalene functionalized diketopyrrolopyrrole based sensitizers for efficient hydrogen production
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| Creator |
Narayanaswamy, K.
Tiwari, Amritanjali Mondal, Indranil Pal, Ujjwal Niveditha, S. Bhanuprakash, K. Singh, Surya Prakash |
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| Subject |
Chemistry
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| Description |
We have designed and synthesized two new diketopyrrolopyrrole (DPP) based organic sensitizers (DPPCA and DPPCN) with the dithiafulvalene (DTF) unit as donor and cyanoacrylic acid/malononitrile as acceptor moieties. These dyes showed excellent efficiency of photocatalytic hydrogen production over a Pt–TiO2 composite via solar-induced water splitting. The sensitizers showed broad absorptions over the wide visible regime (500–800 nm). In DPPCN, the malononitrile moiety led to strong intra-molecular charge transfer, as evidenced by red shifted (∼24 nm) absorption maxima with highly enhanced molar absorptivity (108[thin space (1/6-em)]190 M−1 cm−1). The electrochemical characterization of as-prepared sensitizers confirmed the feasible electron injection from the dye to the TiO2 conduction band (CB) which has been further validated by theoretical studies. In this study, the rate of the photocatalytic activity was found to be dependent on the acceptor part of the dye molecule as DPPCN sensitized Pt–TiO2 (DNPT) exhibited remarkable (1208 μmol) hydrogen evolution yield in comparison to DPPCA sensitized Pt–TiO2 (DAPT) (840 μmol). The rigid DPP core made the sensitizers significantly photo-stable as affirmed by their high hydrogen production efficiency over 80 h of prolonged irradiation. As predicted from density functional theory (DFT) calculations, ground state geometry of the dyes was almost planar, facilitating continuous conjugation throughout the molecule. Time-dependent DFT (TD-DFT) calculations were also carried out to make clear the understanding of charge transfer transition of the dye molecules.
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| Publisher |
Royal Society of Chemistry
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| Date |
2015
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| Type |
Article
PeerReviewed |
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| Identifier |
Narayanaswamy, K. and Tiwari, Amritanjali and Mondal, Indranil and Pal, Ujjwal and Niveditha, S. and Bhanuprakash, K. and Singh, Surya Prakash (2015) Dithiafulvalene functionalized diketopyrrolopyrrole based sensitizers for efficient hydrogen production. Physical Chemistry Chemical Physics, 17. pp. 13710-13718.
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| Relation |
http://cmeri.csircentral.net/211/
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