Coadsorption of Cd(II) and oxalate ions at the TiO2/electrolyte solution interface.

The study of the adsorptions of cadmium and oxalate ions at the titania/electrolyte interface and the changes of the electrical double layer (edl) structure in this system are presented. The adsorption of cadmium or oxalate ions was calculated from an uptake of their concentration from the solution. The concentration of Cd(II) or oxalate ions in the solution was determined by radiotracer method. For labeling the solution 14C and 115Cd isotopes were used. Coadsorption of Cd(II) and oxalic ions was determined simultaneously. Besides, the main properties of the edl, i.e., surface charge density and zeta potential were determined by potentiometer titration and electrophoresis measurements, respectively. The adsorption of cadmium ions increases with pH increase and shifts with an increase of the initial concentration of Cd(II) ions towards higher pH values. The adsorption process causes an increase of negatively charged sites on anatase and a decrease of the zeta potential with an increase of initial concentration of these ions. The adsorption of oxalate anions at the titania/electrolyte interface proceeds through the exchange with hydroxyl groups. A decrease of pH produces an increase of adsorption of oxalate ions. The processes of anion adsorption lead to increase the number of the positively charged sites at the titania surface. However, specific adsorption of bidenate ligand as oxalate on one surface hydroxyl group may form inner sphere complexes on the metal oxide surface and may overcharge the compact part of the edl. The presence of oxalate ions in the system affects the adsorption of Cd(II) ions on TiO2, increasing the adsorption at low pH range and decreasing the adsorption at high pH range. Using adsorption as a function of pH data, some characteristic parameters of adsorption envelope were calculated.