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Biphasic water splitting by osmocene.

Proceedings of the National Academy of Sciences of the United States of America (2012-06-06)
Peiyu Ge, Tanya K Todorova, Imren Hatay Patir, Astrid J Olaya, Heron Vrubel, Manuel Mendez, Xile Hu, Clémence Corminboeuf, Hubert H Girault
ABSTRACT

The photochemical reactivity of osmocene in a biphasic water-organic solvent system has been investigated to probe its water splitting properties. The photoreduction of aqueous protons to hydrogen under anaerobic conditions induced by osmocene dissolved in 1,2-dichloroethane and the subsequent water splitting by the osmocenium metal-metal dimer formed during H(2) production were studied by electrochemical methods, UV-visible spectrometry, gas chromatography, and nuclear magnetic resonance spectroscopy. Density functional theory computations were used to validate the reaction pathways.

MATERIALS
Product Number
Brand
Product Description

Supelco
1,2-Dichloroethane, analytical standard
Sigma-Aldrich
1,2-Dichloroethane, anhydrous, 99.8%
Sigma-Aldrich
1,2-Dichloroethane, SAJ first grade, ≥99.0%
Sigma-Aldrich
1,2-Dichloroethane, JIS special grade, ≥99.5%
Supelco
1,2–Dichloroethane solution, certified reference material, 200 μg/mL in methanol
Sigma-Aldrich
1,2-Dichloroethane, ACS reagent, ≥99.0%