Photoelectrochemistry of Tris(bipyridyl)ruthenium(II) covalently attached to n-type SnO/sub 2/
Ru(bpy)/sub 3//sup 2 +/ (bpy = 2,2'-bipyridyl) has been covalently attached to n-type SnO/sub 2/ via condensation of surface hydroxyl groups with ruthenium 4-(trichlorosilylethyl)-4'-methyl-2,2'-bipyridine)bis(2,2'-bipyridine) bis(hexafluorophosphate)). A thick coating (approx. 1000 layers, based on the surface hydroxyl group concentration) was produced, presumably via oligomerization of hydrolyzed -SiCl/sub 3/ groups. The coating, which was stable to organic solvents as well as to aqueous acids and bases, gave reversible cyclic voltammograms, with peak potentials shifted slightly from those of aqueous Ru(bpy)/sub 3//sup 2 +/, but the number of electroactive molecules corresponded only to a few layers. The coated electrode gave a photocurrent about twice that observed for SnO/sub 2/ in contact with aqueous 4 mM Ru(bpy)/sub 3//sup 2 +/, with a slightly red-shifted excitation spectrum. Only a small fraction of the electroactive molecules appeared to participate in excited-state electron transfer, although a steady-state current was supported, presumably by slow electron transfer from the outer layers. Prolonged illumination produces extensive hydrolysis of the outer layers of the coating, but a modest reduction of electroactivity, and only a slight decrease in photocurrent. The photocurrent increases with applied potential, then reaches a plateau, and falls off again near the reduction potential of Ru(bpy)/sub 3//sup 2 +/*; the falloff is attributed to back-electron transfer via tunneling through the thin space charge layer.
- Research Organization:
- Princeton Univ., NJ
- OSTI ID:
- 6861614
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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AZINES
BIPYRIDINES
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
CONVERSION
COVALENCE
DECOMPOSITION
ELECTROCHEMISTRY
ELECTRODES
ELECTROLYSIS
ELECTRON TRANSFER
ENERGY CONVERSION
ENERGY LEVELS
EXCITED STATES
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROGEN PRODUCTION
HYDROLYSIS
LYSIS
MATERIALS
N-TYPE CONDUCTORS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOELECTROLYSIS
PHOTOLYSIS
PYRIDINES
RUTHENIUM COMPLEXES
SEMICONDUCTOR MATERIALS
SILICON CHLORIDES
SILICON COMPOUNDS
SOLAR ENERGY CONVERSION
SOLVOLYSIS
TIN COMPOUNDS
TIN OXIDES
TRANSITION ELEMENT COMPLEXES