Charge Properties of TiO₂ Nanotubes in NaNO₃ Aqueous Solution

Charging of material surfaces in aqueous electrolyte solutions is one of the most important processes in the interactions between biomaterials and surrounding tissue. Other than a biomaterial, titania nanotubes (TiO₂ NTs) represent a versatile material for numerous applications such as heavy metal adsorption or photocatalysis. In this article, the surface charge properties of titania NTs in NaNO₃ solution were investigated through electrophoretic mobility and polyelectrolyte colloid titration measuring techniques. In addition, we used high-resolution transmission electron microscopy imaging to determine the morphology of TiO₂ NTs. A theoretical model based on the classical density functional theory coupled with the charge regulation method in terms of mass action law was developed to understand the experimental data and to provide insights into charge properties at different physical conditions, namely, pH and NaNO₃ concentration. Two intrinsic protonation constants and surface site density have been obtained. The electrostatic properties of the system in terms of electrostatic potentials and ion distributions were calculated and discussed for various pH values. The model can quantitatively describe the titration curve as a function of pH for higher bulk salt concentrations and the difference in the equilibrium amount of charges between the inner and outer surfaces of TiO₂ NTs. Calculated counterion (NO₃^–) distributions show a pronounced decrease of NO₃^– ions for high bulk pH (both inside and outside TiO₂ NT) because of the strong electric field. With the decrease of bulk pH or the increase of the salt concentration, NO₃^– is able to accumulate near the TiO₂ NTs surfaces