Mechanism of the formation of dihydrogen from the photoinduced reactions of tris(bipyridine)ruthenium(II) with tris(bipyridine)rhodium(III)

Journal Article · Wed Dec 05 04:00:00 EST 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00519a040· OSTI ID:5666812

Brown, G M; Chan, S F; Creutz, C; Schwarz, H A; Sutin, N

Visible light irradiation of aqueous solutions of Ru(bpy)/sub 3//sup 2 +/, Rh(bpy)/sub 3//sup 3 +/, triethanolamine TEOA/TE OAH/sup +/ (pH 8.1), and K/sub 2/PtCl/sub 4/ (or K/sub 2/PtCl/sub 6/) yields dihydrogen with a quantum yield of up to 0.11 +- 0.01 mol einstein/sup -1/ depending on the conditions used. The dihydrogen is the end product of a sequence of electron-transfer reactions. Ru(bpy)/sub 3//sup 2 +/ formed by visible light absorption is oxidized by Rh(bpy)/sub 3//sup 3 +/ to produce Rh(bpy)/sub 3//sup 2 +/ and Ru(bpy)/sub 3//sup 3 +/. The latter is rapidly reduced by TEOA. In the absence of platinum, the rhodium(II) disproportionates to give rhodium(III) and rhodium(I); in the presence of platinum, the rhodium(II) may either disproportionate or yield dihydrogen. Observations on the photochemical and dark reactions in this system are reported. The rhodium system is more expensive than that based on methylviologen and is subject to efficiency-lowering side reactions. 1 figure. (DP)

• Research Organization: Brookhaven National Lab., Upton, NY
• OSTI ID: 5666812
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:25; ISSN JACSA
• Country of Publication: United States
• Language: English

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08 HYDROGEN
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Photobiological
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ALKALI METAL COMPOUNDS
AQUEOUS SOLUTIONS
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
COMPLEXES
CONVERSION
DISPERSIONS
ELECTROLYSIS
ELECTRON TRANSFER
ENERGY CONVERSION
HETEROCYCLIC COMPOUNDS
HYDROGEN PRODUCTION
IRRADIATION
LYSIS
MIXTURES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOELECTROLYSIS
POTASSIUM COMPOUNDS
PYRIDINES
RHODIUM COMPLEXES
RUTHENIUM COMPLEXES
SOLAR ENERGY CONVERSION
SOLUTIONS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES