Plasmonic Aerogels as a Three-Dimensional Nanoscale Platform for Solar Fuel Photocatalysis

We use plasmonic Au-TiO₂ aerogels as a platform in which to marry synthetically thickened particle-particle junctions in TiO₂ aerogel networks to Au∥TiO₂ interfaces and then investigate their cooperative influence on photocatalytic hydrogen (H₂) generation under both broadband (i.e., UV + visible light) and visible-only excitation. In doing so, we elucidate the dual functions that incorporated Au can play as a water reduction cocatalyst and as a plasmonic sensitizer. We also photodeposit non-plasmonic Pt cocatalyst nanoparticles into our composite aerogels in order to leverage the catalytic water-reducing abilities of Pt. This Au-TiO₂/Pt arrangement in three dimensions effectively utilizes conduction-band electrons injected into the TiO₂ aerogel network upon exciting the Au SPR at the Au∥TiO₂ interface. The extensive nanostructured high surface-area oxide network in the aerogel provides a matrix that spatially separates yet electrochemically connects plasmonic nanoparticle sensitizers and metal nanoparticle catalysts, further enhancing solar-fuels photochemistry. We compare the photocatalytic rates of H₂ generation with and without Pt cocatalysts added to Au-TiO₂ aerogels and demonstrate electrochemical linkage of the SPR-generated carriers at the Au∥TiO₂ interfaces to downfield Pt nanoparticle cocatalysts. Finally, we investigate visible light-stimulated generation of conduction band electrons in Au-TiO₂ and TiO₂ aerogels using ultrafast visible pump/IR probe spectroscopy. Substantially more electrons are produced at Au-TiO₂ aerogels due to the incorporated SPR-active Au nanoparticle, whereas the smaller population of electrons generated at Au-free TiO₂ aerogels likely originate at shallow traps in the high surface-area mesoporous aerogel.