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We report on the systematic investigation of the role of surface nanoscaleroughness and morphology on the charging behaviour of nanostructured titania(TiO2) surfaces in aqueous solutions. IsoElectric Points (IEPs) of surfaceshave been characterized by direct measurement of the electrostatic double layerinteractions between titania surfaces and the micrometer-sized spherical silicaprobe of an atomic force microscope in NaCl aqueous electrolyte. The use of acolloidal probe provides well-defined interaction geometry and allowseffectively probing the overall effect of nanoscale morphology. By usingsupersonic cluster beam deposition to fabricate nanostructured titania films,we achieved a quantitative control over the surface morphological parameters.We performed a systematical exploration of the electrical double layerproperties in different interaction regimes characterized by different ratiosof characteristic nanometric lengths of the system: the surface rms roughnessRq, the correlation length {\xi} and the Debye length {\lambda}D. We observed aremarkable reduction by several pH units of IEP on rough nanostructuredsurfaces, with respect to flat crystalline rutile TiO2. In order to explain theobserved behavior of IEP, we consider the roughness-induced self-overlap of theelectrical double layers as a potential source of deviation from the trendexpected for flat surfaces.

Nanoscale roughness and morphology affect the IsoElectric Point of titania surfaces