Journal of Physical Chemistry B, Vol.101, No.50, 10791-10800, 1997
Visible-Light-Induced and Long-Lived Charge Separation in a Transparent Nanostructured Semiconductor Membrane Modified by an Adsorbed Electron-Donor and Electron-Acceptor
The preparation of transparent nanostructured TiO2 (anatase) membranes is described. Detailed characterization shows these membranes to be 50 mu m thick nanoporous-nanocrystalline structures with associated values for porosity and surface roughness of 50% and 5000, respectively. Modification of these membranes by coadsorption of a ruthenium complex, bis [(4,4’-dicarboxy-2,2’-bipyridine)(4,4’-dimethyl-2,2’-bipyridine)-ruthenium(II)] dichloride (I), and of a viologen, 1-ethyl-1’-[(4-carboxy-3-hydroxyphenyl)methyl]-4,4’-bipyridinium perchlorate (II), is also described. Detailed studies show that visible-light-induced electron transfer by electronically excited I to the conduction band of the nanostructured TiO2 membrane is followed by membrane mediated electron transfer to coadsorbed II. Detailed studies also show that, as a consequence of the rectifying properties of the semiconducting membrane, charge separation is long-lived, The possible significance of these findings for the development of a practical water splitting device is considered.
Keywords:CONDUCTION-BAND ELECTRONS;OPTICAL ELECTROCHEMISTRY;SURFACE CHELATION;COLLOIDAL TIO2;VIOLOGEN;FILMS;SPECTROSCOPY;INTERFACE;STATE;CONVERSION