Photoinduced water splitting via benzoquinone and semiquinone sensitisation

Tolga N.V. Karsili, Deniz Tuna, Johannes Ehrmaier, Wolfgang Domcke

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

The splitting of water into H and OH radicals by sensitisation of a redox-active chromophore with sunlight may eventually become a viable way of producing unlimited, clean and sustainable energy. In this work, we explore the possibility of photo-oxidation of water via sensitisation of benzoquinone with ultraviolet (UV) light in the hydrogen-bonded complex of benzoquinone with a single water molecule. Using state-of-the-art quantum chemical calculations, the mechanisms of electron/proton transfer reactions between photoexcited benzoquinone and water are characterised. In the benzoquinone-H2O complex, photoexcitation of the chromophore leads to the population of locally excited ππ∗ and nπ∗ singlet states, which are coupled to hitherto unknown charge-transfer states. In the latter, an electron is transferred from the oxygen atom of the water molecule to the lowest π∗ orbital of benzoquinone. These charge-separated states drive the transfer of a proton from the water molecule to the carbonyl acceptor site, yielding the semiquinone-OH biradical. Upon absorption of a second UV photon, the semiquinone radical may undergo O-H bond fission, which generates an H radical and restores the benzoquinone photocatalyst. Our computational results shed light on long-standing questions regarding the nature of the photoreactive electronic states in the aqueous photochemistry of benzoquinone.

Original languageEnglish
Pages (from-to)32183-32193
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume17
Issue number48
DOIs
StatePublished - 2015

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