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The effect of mild reduction treatment on TiO 2 surfaces has been investigated by the ZPC (zero point of charge) potentiometric technique. Different extents of reduction result in a series of oxides distinguished either by their adsorption characteristics or electrochemical properties. Non-stoichiometric surface oxide formation has been demonstrated by X-ray diffraction and flat-band potential (V fb ) measurements. The generation of surface states with essentially acid–base characteristics has been shown to be a determining factor in the photo-oxidation–photodecomposition of water. A number of hypotheses relating to the nature of the adsorption-determining sites have been advanced.