Engineering the Absorption and Field Enhancement Properties of Au-TiO₂ Nanohybrids via Whispering Gallery Mode Resonances for Photocatalytic Water Splitting

Recently, surface plasmon resonance (SPR) effects have been widely used to construct photocatalysts which are active in the visible spectral region. Such plasmonic photocatalysts usually comprise a semiconductor material transparent in the visible range (such as TiO₂) and plasmonic nano-objects (e.g., Au nanoparticles (Au NPs)). Specific SPRs, though, only partially cover the visible spectrum and feature weak light absorption. Here, we explore the unique role played by whispering gallery mode (WGM) resonances in the expression of the photocatalytic activity of plasmonic photocatalysts. Using numerical simulations, we demonstrate that, by solely exploiting a proper geometrical arrangement and WGM resonances in a TiO₂ sphere, the plasmonic absorption can be extended over the entire visible range and can be increased by more than 40 times. Furthermore, the local electric field at the Au-TiO₂ interface is also considerably enhanced. These results are experimentally corroborated, by means of absorption spectroscopy and Raman measurements. Accordingly, such WGM-assisted plasmonic photocatalysts, when employed in water splitting experiments, exhibit enhanced activity in the visible range. Our findings show a promising and straightforward way to design full solar spectrum photocatalysts.