Plasmon-Driven Modulation of Reaction Pathways of Individual Pt-Modified Au Nanorods.

Understanding the underlying kinetic mechanism of plasmon-enhanced catalysis is important for designing optimized bimetal nanostructures. Here, we characterize product formation rate at both the single-particle and ensemble level. The single-particle measurement allows us to reveal the underlying catalytic kinetic mechanisms of a bimetal nanostructure. Combining this with ensemble observations of two different catalytic behaviors of this catalyst with and without illumination shows that energetic charge carriers induce a transition from a competitive reactant adsorption type to a noncompetitive adsorption type, which leads to the suppression of catalytic rate decay at high reactant concentration. Theoretical modeling as well as analysis of hole acceptability of scavengers on Pt and Au surfaces indicates that the Pt light absorptivity is enhanced near Au and the energetic charges may form directly from the Pt part of the Au-Pt nanostructure. The presented study deepens our understanding of plasmon-enhanced catalysis by bimetal nanostructures.