Self-Optimized Catalysts: Hot-Electron Driven Photosynthesis of Catalytic Photocathodes

Photogenerated hot electrons from plasmonic nanostructures are very promising for photocatalysis, mostly due to their potential for enhanced chemical selectivity. Here, we present a self-optimized fabrication method of plasmonic photocathodes using hot-electron chemistry, for enhanced photocatalytic efficiencies. Plasmonic Au/TiO₂ nanoislands are excited at their surface plasmon resonance to generate hot electrons in an aqueous bath containing a platinum (cocatalyst) precursor. Hot electrons drive the deposition of Pt cocatalyst nanoparticles, without any nanoparticle functionalization and negligible applied bias, close to the hotspots of the plasmonic nanoislands. The presence of TiO₂ is crucial for achieving higher chemical reaction rates. The Au/TiO₂/Pt photocathodes synthesized using hot-electron chemistry show a photocatalytic activity of up to 2 times higher than that of a control made with random electrodeposited Pt nanoparticles. This light-driven positioning of the cocatalyst close to the same positions where hot electrons are most efficiently generated and transferred represents a novel and simple method for synthesizing complex, self-optimized photocatalytic nanostructures with improved efficiency and selectivity.