Investigating the influence of silver state on electronic properties of Ag/Ag2O/TiO2 heterojunctions prepared by photodeposition

Abstract Two series of Ag-TiO2 photocatalysts were prepared with the use of photodeposition method with variation of the irradiation time and precursor concentration. The obtained photocatalysts were studied by XRD, Raman spectroscopy, HR TEM, UV-Vis spectroscopy, and low-temperature N2 desorption method. It has been consequently found that the optical properties of the resulting catalysts differ significantly: the positions of surface plasmon resonance peaks red-shifted with the increase in precursor concentration. At the same time, optical absorption of the samples increases with both precursor concentration and irradiation time. Photocatalytic activity for the obtained catalysts was evaluated in decolorization of Rhodamine B with the use of Xe arc lamp (250 W) with and without λ > 420 nm light filter. Radical trap experiments have shown that the amount of both superoxide anions and hydroxyl radicals increased in full spectrum of the lamp, with the latter being absent in the reaction mixture during visible light photocatalysis. Comparison of different Ag-TiO2 catalysts has also been made, with 1-Ag-90 min sample being the most active in full spectrum, and 3-Ag-90 min demonstrating the highest conversion in visible light attributed to the increased generation of superoxide species on the surface of Ag clusters. Controversially, 1-Ag-45 min sample showed the lowest activity in full spectrum being surpassed even by unmodified TiO2, but reached the highest rate constant value in visible light. This effect can be related to advanced electronic interaction between Ag plasmonic nanoparticles and titania support in the presence of sensitizer compound, and the formation of Ag/Ag2O composite system on the surface of titania. Influence of the state of silver on photocatalytic activity and mechanism details is discussed with special attention to irradiation wavelengths.