Single-atom dopants in plasmonic nanocatalysts

TL;DR

This study uses first-principles calculations to show that single-atom dopants in plasmonic nanoparticles can significantly alter local hot-carrier generation without affecting overall plasmonic response, enabling tunable hot-carrier properties.

Contribution

It demonstrates how dopant elements influence local hot-carrier generation in plasmonic nanoparticles, providing a pathway for tailored plasmonic catalysis.

Findings

Hot-hole generation is affected by dopant element.

D-electron states of dopants determine hot-hole energies.

Overall plasmonic response remains largely unchanged.

Abstract

Bimetallic nanostructures combining plasmonic and catalytic metals are promising for tailoring and enhancing plasmonic hot-carrier generation utilized in plasmonic catalysis. In this work, we study the plasmonic hot-carrier generation in noble metal nanoparticles (Ag, Au, Cu) with single-atom dopants (Ag, Au, Cu, Pd, Pt) with first-principles time-dependent density-functional theory calculations. Our results show that the local hot-carrier generation at the dopant atom is significantly altered by the dopant element while the plasmonic response of the nanoparticle as a whole is not significantly affected. In particular, hot holes at the dopant atom originate from the discrete d-electron states of the dopant. The energies of these d-electron states, and hence those of the hot holes, depend on the dopant element, which opens up the possibility to tune hot-carrier generation with suitable dopants.