Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures.

The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝ intensity(n), with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.