Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Hot electrons generated in metal nanoparticles can drive chemical reactions and selectively deposit cocatalyst materials on the plasmonic hotspots, the areas where the decay of plasmons takes place and the hot electrons are created. While hot electrons have been extensively used for nanomaterial formation, the utilization of hot holes for simultaneous cocatalyst deposition has not yet been explored. Herein, we demonstrate that hot holes can drive an oxidation reaction for the deposition of the manganese oxide (MnO) cocatalyst on different plasmonic gold (Au) nanostructures on a thin titanium dioxide (TiO₂) layer, excited at their surface plasmon resonance. An 80% correlation between the hot-hole deposition sites and the simulated plasmonic hotspot location is showed when considering the typical hot-hole diffusion length. Simultaneous deposition of more than one cocatalyst is also achieved on one of the investigated plasmonic systems (Au plasmonic nanoislands) through the hot-hole oxidation of a manganese salt and the hot-electron reduction of a platinum precursor in the same solution. These results add more flexibility to the use of hot carriers and open up the way for the design of complex photocatalytic nanostructures.