Theoretical Design of Photocatalytic System with Hot Electron of Noble Metal Nanoparticle: Effect of Atomic Size Defects

Abstract

By using discrete dipole approximation (DDA) calculation, we investigated the effect of surface defects of atomic size, which might be fundamentally important issue to realize the performance of heterogeneous catalysis in utilizing the hot electron (HE) phenomenon. The cubic-shaped gold nanostructure was considered to investigate the sole effect of defects on the HE generation. Interestingly, in monomer system, silver-doped defect enhanced the generation and lifetime of HEs. In order to improve the generation of HEs, dimer structure was considered. Although the absorption enhancement was reduced, the amount of HE generated was increased by plasmon coupling effect. Especially, the generation of HEs was maximized when the silver was doped in the direction of propagating light, but not the gap junction. It indicates that the silver-doped defect can provide favorable site for photocatalytic reaction. This theoretical study shows a promising result in terms of improving the performance of plasmon-mediated photocatalyst using HEs.