Interactions of Plasmonic Silver Nanoparticles with High Energy Sites on Multi-Faceted Rutile TiO2 Photoanodes

The plasmonic interactions between silver nanoparticles and various rutile TiO2 facets are studied by correlating Advanced Electron Microscopy and Electrochemical Impedance Spectroscopy (EIS) to help design a route towards an optimised polycrystalline film fabrication. By using an Electron Backscatter Diffraction (EBSD) detector, it was determined that using HF as directing agent during the hydrothermal growth of TiO2 promotes the formation of high-angle grain boundaries. Silver photodeposition occurs preferentially at these boundaries, consistent with the presence of high energy sites on the (100)-oriented rutile TiO2 nanorods. Further EIS study showed an increase in the photoelectrochemical activity in the visible range of the solar spectrum for the samples consisting of silver nanoparticles deposited on these grain boundaries.