control of surface and ζ potentials on nanoporous tio2 films by .pdfVIP

6094 Langmuir 2000, 16, Control of Surface and Potentials on Nanoporous TiO2 Films by Potential-Determining and Specifically Adsorbed Ions Bryce P. Nelson,† Roberto Candal,‡,§ Robert M. Corn,† and Marc A. Anderson*,‡ Water Chemistry Program, University of WisconsinMadison, 660 North Park Street, Madison, Wisconsin, 53706, and Department of Chemistry, University of WisconsinMadison, 1101 University Avenue, Madison, Wisconsin 53706 Received August 26, 1999. In Final Form: April 17, 2000 The effect of a specifically adsorbed ion, phosphate, on the electrochemical response and adsorption properties of nanocrystalline TiO2 is examined. Phosphate is known to affect the potential, as measured by electrophoretic mobility, by changing the charge of the oxide surface. The adsorption of a cationic probe molecule, thionine, onto TiO2 was monitored with an in-situ cell using UVvis spectroscopy. The adsorption of the cationic dye molecule was found to be governed by changes in the potential, whether the potential was modified by pH or by changes in phosphate concentration. Onset potential measurements were used to estimate the flat-band potential of a Ti/TiO2 electrode. The flat-band potential results for the electrode showed a nearly Nernstian response to changes in the pH for a broad pH range. The addition of phosphate had no effect on the onset potential or on the shape of the photocurrent/potential curve. Flat-band potentials determined by MottSchottky analysis in the absence of phosphate were Nernstian only for pH 37,