Details

Autor(en) / Beteiligte

• Rivier, Lucie
• Peljo, Pekka
• Vannay, Laurent A. C.
• Gschwend, Grégoire C.
• Méndez, Manuel A.
• Corminboeuf, Clémence
• Scanlon, Micheál D.
• Girault, Hubert H.

Titel

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling

Ist Teil von

• Angewandte Chemie International Edition, 2017-02, Vol.56 (9), p.2324-2327

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2017

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp2*RuII (Cp*=C5Me5), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp2*RuIII]+ species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions— especially the use of weakly coordinating solvent and counterions—are discussed. A Cp2*RuII single molecule photogenerated hydrogen with an internal quantum yield of 25 %. Cp2*RuII was electrochemically regenerated in situ and spectroscopic studies enabled deconvolution of the operating reaction mechanism. Combined with electrochemical recycling, metallocene electron donors such as Cp2*RuII could work in tandem with a water oxidation catalyst to photoproduce H2 from water.