Doping of photoactive TiO2 films by DC Plasma Electrolytic Oxidation: effect of transition metals

Several beneficial features maintain TiO2 in the top list of viable materials for photocatalytic purposes. However, its relatively large band-gap (3.0-3.2eV) still hampers practical applications under sunlight. This work explores Direct Current (DC) Plasma Electrolytic Oxidation (PEO) of titanium as a fast, easily-scalable and single-step tool to synthesise doped TiO2 photoanodes with controlled morphology, crystalline structure and thickness. Zn-, Cu- and Fe-doped crystalline TiO2 films were obtained in H2SO4 aqueous solutions containing ZnSO4, CuSO4 and FeSO4 precursors, respectively. As-prepared TiO2 films showed a porous and homogeneous sponge-like surface morphology, typical of PEO-produced oxides, and a crystalline phase structure consisting of a mixture of anatase and rutile phases. The anatase content varied in the 54-100% range and correspondingly the band-gap energy was in the 2.85-3.07eV range. Doped oxides prepared with a low concentration of the metal precursors showed monochromatic incident-photon-to-current-efficiency (IPCE) values exceeding those obtained with pristine TiO2 by up to 24%, best performing in the order Zn- > Cu- > Fe-doped TiO2. Photocurrent under polychromatic UV-Vis irradiation showed an analogous trend and the estimated efficiency of solar-light harvesting was in the 0.3-4% range, with Zn- ≈ Cu- > Fe-doped TiO2. Although the superior performance of the PEO-prepared metal-doped TiO2 could not be fully confirmed by photoelectrocatalytic oxidation tests of organics, the present investigation showed the viability of DC PEO for the synthesis of metal-doped TiO2 photoanodes.