Thin Film Nanocrystalline TiO2 Electrodes: Dependence of Flat Band Potential on pH and Anion Adsorption

Thin nanocrystalline TiO2 films were produced on ITO conductive glass by dip-coating of a sol-gel TiO2 precursor. The transparent films were characterized from the optical and structural point of view with UV-Vis, Spectroscopic Ellipsometry, Raman and X-ray photoelectron spectroscopies, the roughness of the coating by AFM. The changes in the electrochemical properties features of ITO/TiO2 electrodes were evaluated in the presence of different electrolytes (KCl, Na2 SO4 and phosphate buffer) with the aim to clarify the role of the ion adsorption on the structure of the electrical double layer. Electrochemical tests (Cyclic Voltammetry, CV, and Impedance Electrochemical Spectroscopy, EIS) showed a strong influence of the electrolyte properties on the semiconductor band edge position in the electrochemical scale and on band bending. The CV profiles recorded can be explained by considering that the interface capacity is due to the charging of surface states (e.g., Ti(IV) surface sites coordinated by oxygen atoms, =Ti-OH or Ti-O-Ti). The surface charge is strongly affected also by the density and nature of adsorbed ions and by dissociation of surficial OH. Of interest the fact that for the produced nanocrystalline electrodes the flat band potential, measured from the Mott-Schottky analysis of the space charge layer capacity obtained with EIS, showed a non Nernstian behavior with the pH probably caused by a change in the surface acidity as a consequence of specific anion adsorption. The modulation of flat band potential with adsorbed ions is of interest for many applications, in particular for photocatalysis (change in the redox potential of photogenerated carriers) and for photovoltaic applications like DSSC (change in the photopotentials)