A plasmonic photocatalyst consisting of silver nanoparticles embedded in titanium dioxide

J Am Chem Soc. 2008 Feb 6;130(5):1676-80. doi: 10.1021/ja076503n. Epub 2008 Jan 12.


Titanium dioxide (TiO2) displays photocatalytic behavior under near-ultraviolet (UV) illumination. In another scientific field, it is well understood that the excitation of localized plasmon polaritons on the surface of silver (Ag) nanoparticles (NPs) causes a tremendous increase of the near-field amplitude at well-defined wavelengths in the near UV. The exact resonance wavelength depends on the shape and the dielectric environment of the NPs. We expected that the photocatalytic behavior of TiO2 would be greatly boosted if it gets assisted by the enhanced near-field amplitudes of localized surface plasmon (LSP). Here we show that this is true indeed. We named this new phenomenon "plasmonic photocatalysis". The key to enable plasmonic photocatalysis is to deposit TiO2 on a NP comprising an Ag core covered with a silica (SiO2) shell to prevent oxidation of Ag by direct contact with TiO2. The most appropriate diameter for Ag NPs and thickness for the SiO2 shell giving rise to LSP in the near UV were estimated from Mie scattering theory. Upon implementing a device that took these design considerations into account, the measured photocatalytic activity under near UV illumination of such a plasmonic photocatalyst, monitored by decomposition of methylene blue, was enhanced by a factor of 7. The enhancement of the photocatalytic activity increases with a decreased thickness of the SiO2 shell. The plasmonic photocatalysis will be of use as a high performance photocatalyst in nearly all current applications but will be of particular importance for applications in locations of minimal light exposure.